JP7377174B2 - Fireproof sheet for wallpaper lining - Google Patents
Fireproof sheet for wallpaper lining Download PDFInfo
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- JP7377174B2 JP7377174B2 JP2020107011A JP2020107011A JP7377174B2 JP 7377174 B2 JP7377174 B2 JP 7377174B2 JP 2020107011 A JP2020107011 A JP 2020107011A JP 2020107011 A JP2020107011 A JP 2020107011A JP 7377174 B2 JP7377174 B2 JP 7377174B2
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- 239000000835 fiber Substances 0.000 claims description 157
- 239000000463 material Substances 0.000 claims description 120
- 239000010954 inorganic particle Substances 0.000 claims description 109
- 238000000576 coating method Methods 0.000 claims description 82
- 239000011248 coating agent Substances 0.000 claims description 79
- 239000011230 binding agent Substances 0.000 claims description 57
- 239000012210 heat-resistant fiber Substances 0.000 claims description 55
- 239000003365 glass fiber Substances 0.000 claims description 48
- 239000000853 adhesive Substances 0.000 claims description 36
- 230000001070 adhesive effect Effects 0.000 claims description 35
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 29
- 230000003746 surface roughness Effects 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 29
- 229920000915 polyvinyl chloride Polymers 0.000 description 29
- 239000007788 liquid Substances 0.000 description 27
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- 239000000843 powder Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- -1 maleic anhydride Chemical class 0.000 description 14
- 239000005995 Aluminium silicate Substances 0.000 description 11
- 235000012211 aluminium silicate Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000004760 aramid Substances 0.000 description 7
- 229920003235 aromatic polyamide Polymers 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000009970 fire resistant effect Effects 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000004113 Sepiolite Substances 0.000 description 5
- 238000012937 correction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 235000019355 sepiolite Nutrition 0.000 description 5
- 229910052624 sepiolite Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920013820 alkyl cellulose Polymers 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 206010061592 cardiac fibrillation Diseases 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002600 fibrillogenic effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000003702 image correction Methods 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000004439 roughness measurement Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- HSAOVLDFJCYOPX-UHFFFAOYSA-N 2-[4-(1,3-benzothiazol-2-yl)phenyl]-1,3-benzothiazole Chemical compound C1=CC=C2SC(C3=CC=C(C=C3)C=3SC4=CC=CC=C4N=3)=NC2=C1 HSAOVLDFJCYOPX-UHFFFAOYSA-N 0.000 description 1
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101000638161 Homo sapiens Tumor necrosis factor ligand superfamily member 6 Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 102100031988 Tumor necrosis factor ligand superfamily member 6 Human genes 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003190 poly( p-benzamide) Polymers 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Nonwoven Fabrics (AREA)
- Paper (AREA)
Description
本発明は、家屋等に使用される内装用の壁紙裏打ち用耐火シートに関するものであり、発泡ポリ塩化ビニル樹脂（発泡塩ビゾル）塗工の壁紙裏打ち用耐火シートに好適に用いられる。 The present invention relates to a fireproof sheet for lining interior wallpaper used in houses, etc., and is suitably used as a fireproof sheet for lining wallpaper coated with foamed polyvinyl chloride resin (foamed vinyl chloride sol).
建築基準法及び同法施行令によって防火対象となる建築物が定められている。これに該当する商業施設、オフィスビル、医療・福祉施設などを中心に、新築又はリニューアルの際に、壁、天井などの内装制限を受ける物件では、不燃材料認定の防火性能を持つ壁装材料を使用することが要求されている。そのため、防炎性、耐熱性、不燃性等を有する壁装材料がいくつか提案されている。しかし、防炎性、耐熱性、不燃性等の性能を満足すると共に、ポリ塩化ビニル樹脂塗工表面の平坦性が良好で、施工しやすい柔軟性を兼ね備えた壁紙裏打ち用シートは未だ見出されていないというのが現状である。 Buildings that are subject to fire prevention are determined by the Building Standards Act and its enforcement order. For properties that are subject to interior decoration restrictions such as walls and ceilings when newly built or renovated, mainly commercial facilities, office buildings, medical and welfare facilities, etc. that fall under this category, wall covering materials with fire-retardant properties certified as noncombustible materials are used. is required to be used. Therefore, several wall covering materials having flame retardant properties, heat resistance, noncombustibility, etc. have been proposed. However, a wallpaper backing sheet that satisfies performance requirements such as flame retardancy, heat resistance, and noncombustibility, has good flatness of the polyvinyl chloride resin coated surface, and is flexible enough to be easily applied has yet to be found. The current situation is that it is not.
例えば、シート材料として、特許文献１では、ガラス繊維が２０～１００％で、パルプ及び／又はその他の有機繊維が８０～０％である繊維基材シートの間隙部に、無機質充填材と有機系合成樹脂とを混合して付与（附与）したシート材料が開示されている。このように、無機質充填材を使用した場合には、繊維基材シートには、無機質充填材を付与する際の塗工性が優れていることが求められる。また、シート材料には、無機質充填材が脱落する「粉落ち」と呼ばれる現象が発生し難いことが求められる。特許文献１のシート材料は、有機繊維が使用されるため、不燃性が不十分であり、また、有機繊維が使用されない場合、シート強度が弱く、無機質充填材を付与しにくく、塗工性が低いという課題がある。また、無機質充填材のバインダーとして、有機系合成樹脂を使用しており、不燃性と耐熱性が低下する問題点があった。さらに、ポリ塩化ビニル樹脂塗工表面の平坦性も不十分であった。 For example, as a sheet material, Patent Document 1 discloses that an inorganic filler and an organic filler are used in the gaps between fiber base sheets containing 20 to 100% glass fiber and 80 to 0% pulp and/or other organic fibers. A sheet material to which a synthetic resin is mixed and applied is disclosed. In this way, when an inorganic filler is used, the fiber base sheet is required to have excellent coating properties when the inorganic filler is applied. Further, the sheet material is required to be resistant to a phenomenon called "powder drop" in which the inorganic filler falls off. Since the sheet material of Patent Document 1 uses organic fibers, its nonflammability is insufficient, and when organic fibers are not used, the sheet material has low sheet strength, is difficult to add inorganic fillers, and has poor coatability. There is the issue of low Furthermore, an organic synthetic resin is used as a binder for the inorganic filler, which poses the problem of reduced flame resistance and heat resistance. Furthermore, the flatness of the surface coated with polyvinyl chloride resin was also insufficient.
また、光沢を有する難燃紙として、特許文献２では、消炎性ガスを発生する無機粉体を主成分とする難燃塗料を、無機繊維の紙状物に含浸せしめてなるシート状物が開示されている。この難燃紙では、難燃塗料に有機バインダーが使用されているため、不燃性が十分でなく、また、無機粉体の塗工に離型紙が使用されており、生産性が悪く、コスト高になる課題があり、さらに、壁紙用裏打ちシートとしては、柔軟性に欠ける問題点があった。 Furthermore, as a glossy flame-retardant paper, Patent Document 2 discloses a sheet-like material made by impregnating a paper-like material of inorganic fibers with a flame-retardant paint whose main component is an inorganic powder that generates an anti-inflammatory gas. has been done. This flame-retardant paper uses an organic binder in the flame-retardant paint, so it does not have sufficient flame resistance, and release paper is used to coat the inorganic powder, resulting in poor productivity and high costs. Furthermore, as a backing sheet for wallpaper, there was a problem of lack of flexibility.
また、特許文献３では、少なくとも、ガラス繊維、木材パルプ、及びバインダー繊維からなるガラス繊維混抄紙の表面にラテックスを含む樹脂組成物を塗工することが開示されている。このガラス繊維混抄紙は、木材パルプやラテックス等の樹脂組成物を塗工しているため、不燃性や耐火性が低かった。また、発泡ポリ塩化ビニル樹脂表面の平滑性も、クッション床材用としては十分であるものの、壁紙裏打ち用としては不十分であった。 Further, Patent Document 3 discloses that a resin composition containing latex is applied to the surface of a glass fiber mixed paper made of at least glass fibers, wood pulp, and binder fibers. This glass fiber mixed paper had low nonflammability and fire resistance because it was coated with a resin composition such as wood pulp or latex. Furthermore, the surface smoothness of the foamed polyvinyl chloride resin was sufficient for use as a cushion flooring material, but was insufficient for use as a wallpaper lining.
本発明の課題は、無機粒子層の塗工性に優れ、ポリ塩化ビニル樹脂塗工表面の平坦性が良好で、さらに柔軟性と耐火性と不燃性を兼ね備え、粉落ちが少ない壁紙裏打ち用耐火シートを提供することにある。 The object of the present invention is to have an inorganic particle layer with excellent coating properties, a polyvinyl chloride resin coated surface with good flatness, flexibility, fire resistance, and non-combustibility, and a fire resistant wallpaper lining with less powder falling off. The purpose is to provide seats.
上記課題を解決するために鋭意研究した結果、下記発明を見出した。 As a result of intensive research to solve the above problems, the following invention was discovered.
（１）基材と無機粒子層とを含有し、該基材がガラス繊維と湿熱接着性バインダー繊維とフィブリル化耐熱性繊維からなり、基材に含まれる全繊維成分に対して、ガラス繊維の含有率は７５～９５質量％であり、湿熱接着性バインダー繊維の含有率は３～２０質量％であり、フィブリル化耐熱性繊維の含有率は１質量％以上１２質量％以下であり、該無機粒子層が無機粒子と無機バインダーからなり、無機粒子層に含まれる無機バインダーの含有率は、無機粒子の総量に対して、２質量％以上１００質量％以下であり、無機粒子層の含有率（「無機粒子層の塗工量（ｇ／ｍ
２
）／基材坪量（ｇ／ｍ
２
）×１００」で算出される値）は９０質量％以上１６０質量％未満であり、且つ、該無機粒子層が、該基材に含有される繊維の表面を被覆していることを特徴とする壁紙裏打ち用耐火シート。
(1) Contains a base material and an inorganic particle layer, the base material is composed of glass fiber, wet heat adhesive binder fiber, and fibrillated heat-resistant fiber , and the glass fiber is The content is 75 to 95% by mass, the content of moist heat adhesive binder fiber is 3 to 20% by mass, the content of fibrillated heat-resistant fiber is 1% to 12% by mass, and the content of the inorganic The particle layer consists of inorganic particles and an inorganic binder, and the content of the inorganic binder contained in the inorganic particle layer is 2% by mass or more and 100% by mass or less based on the total amount of inorganic particles, and the content of the inorganic particle layer ( The value calculated by "coating amount of inorganic particle layer (g/m 2 )/base weight (g/m 2 ) x 100" is 90% by mass or more and less than 160% by mass, and the inorganic A fireproof sheet for wallpaper lining, characterized in that a particle layer covers the surface of fibers contained in the base material.
（２）該湿熱接着性バインダー繊維がシラノール変性ポリビニルアルコール繊維である上記（１）記載の壁紙裏打ち用耐火シート。 (2) The fireproof sheet for wallpaper lining according to the above (1), wherein the moist heat adhesive binder fiber is a silanol-modified polyvinyl alcohol fiber.
（３）基材に含まれる全繊維成分に対して、該フィブリル化耐熱性繊維の含有率が２質量％以上１０質量％以下である上記（１）又は（２）記載の壁紙裏打ち用耐火シート。 (3) The fireproof sheet for wallpaper lining according to (1) or (2) above, wherein the content of the fibrillated heat-resistant fibers is 2% by mass or more and 10% by mass or less with respect to the total fiber components contained in the base material. .
（４）該壁紙裏打ち用耐火シートの少なくとも片側の面を共焦点レーザー顕微鏡によって表面粗さを計測して得られるコア部のレベル差Ｓｋが５５μｍ以下である上記（１）～（３）のいずれか記載の壁紙裏打ち用耐火シート。 (4) Any of the above (1) to (3), wherein the level difference Sk of the core portion obtained by measuring the surface roughness of at least one side of the fireproof sheet for wallpaper lining using a confocal laser microscope is 55 μm or less. Fireproof sheet for wallpaper lining as described in .
本発明の壁紙裏打ち用耐火シートは、ガラス繊維と湿熱接着性バインダー繊維とフィブリル化耐熱性繊維を含有する基材を含有している。ガラス繊維とフィブリル化耐熱性繊維が絡み合い、絡み合った交点を湿熱接着性バインダー繊維で固定するため、基材の湿潤引張強度が優れており、無機粒子層の塗工性に優れ、無機粒子層形成用塗工液を基材へ塗工する際の操業安定性に優れている。 The fireproof sheet for wallpaper lining of the present invention contains a base material containing glass fibers, moist heat adhesive binder fibers, and fibrillated heat-resistant fibers. Glass fibers and fibrillated heat-resistant fibers are intertwined, and the intertwined intersections are fixed with wet heat adhesive binder fibers, so the base material has excellent wet tensile strength and the inorganic particle layer has excellent coating properties, making it possible to form an inorganic particle layer. Excellent operational stability when applying coating liquid to substrates.
また、無機粒子と無機バインダーを含有する無機粒子層を含有し、且つ、該無機粒子層が、該基材に含有される繊維の表面を被覆することによって、耐火性及び不燃性に優れるという効果を達成できる。そして、基材がフィブリル化耐熱性繊維を含有するため、無機粒子層形成用塗工液の浸透性と液保持性に優れるため、無機粒子の含有率を高めることができ、耐火性及び不燃性を高めることができる。さらに、湿熱接着性バインダー繊維とフィブリル化耐熱性繊維を含有することで、ポリ塩化ビニル樹脂塗工表面の平坦性が良好で、粉落ちが少なく、施工しやすい柔軟性を確保することができる。 Furthermore, by containing an inorganic particle layer containing inorganic particles and an inorganic binder, and by coating the surface of the fibers contained in the base material, the inorganic particle layer has excellent fire resistance and noncombustibility. can be achieved. In addition, since the base material contains fibrillated heat-resistant fibers, it has excellent permeability and liquid retention for the coating liquid for forming an inorganic particle layer, so the content of inorganic particles can be increased, resulting in fire resistance and noncombustibility. can be increased. Furthermore, by containing the wet heat adhesive binder fiber and the fibrillated heat-resistant fiber, the polyvinyl chloride resin coated surface has good flatness, less powder falling off, and flexibility that is easy to apply.
本発明において、壁紙裏打ち用耐火シートは、基材と無機粒子層とを含有し、該基材がガラス繊維と湿熱接着性バインダー繊維とフィブリル化耐熱性繊維を含有し、該無機粒子層が無機粒子と無機バインダーを含有し、且つ、該無機粒子層が、該基材に含有される繊維の表面を被覆していることを特徴とする。本明細書において、「壁紙裏打ち用耐火シート」を「耐火シート」と略記する場合がある。 In the present invention, the fireproof sheet for wallpaper lining contains a base material and an inorganic particle layer, the base material contains glass fibers, a wet heat adhesive binder fiber, and a fibrillated heat-resistant fiber, and the inorganic particle layer contains an inorganic particle layer. It is characterized in that it contains particles and an inorganic binder, and that the inorganic particle layer covers the surface of the fibers contained in the base material. In this specification, "fireproof sheet for wallpaper lining" may be abbreviated as "fireproof sheet".
本発明におけるガラス繊維としては、例えば、チョップドストランド、グラスウール、グラスフレークが挙げられる。折れ難く、基材の形成能があればいずれのガラス繊維でも良い。ガラス繊維の繊維径は、１～１１μｍであることが好ましく、２～８μｍであることがより好ましく、３～７μｍであることがさらに好ましい。繊維径が１μｍ未満の場合、細か過ぎて抄造時に基材からガラス繊維が脱落し、基材の強度及び厚みが不十分となる場合がある。繊維径が１１μｍを超えた場合、ガラス繊維が太くなり過ぎて、基材の隙間が大きくなり、無機粒子層を形成しても、ポリ塩化ビニル樹脂塗工表面の平坦性が損なわれる場合や無機粒子の粉落ちが増加する場合や柔軟性が悪化する場合がある。ガラス繊維の繊維径が１～１１μｍである場合、基材の隙間が細かく、均一となるため、無機粒子層を形成後の粉落ちが少なく、ポリ塩化ビニル樹脂を塗工した表面が平坦となりやすく、さらに、柔軟性も優れた耐火シートになる。 Examples of the glass fiber in the present invention include chopped strands, glass wool, and glass flakes. Any glass fiber may be used as long as it is hard to break and has the ability to form a base material. The fiber diameter of the glass fiber is preferably 1 to 11 μm, more preferably 2 to 8 μm, and even more preferably 3 to 7 μm. If the fiber diameter is less than 1 μm, the glass fibers may fall off from the base material during papermaking because they are too fine, resulting in insufficient strength and thickness of the base material. If the fiber diameter exceeds 11 μm, the glass fibers will become too thick and the gap between the base materials will become large, and even if an inorganic particle layer is formed, the flatness of the polyvinyl chloride resin coated surface may be impaired or the inorganic particles may become too thick. Particle shedding may increase or flexibility may deteriorate. When the fiber diameter of the glass fiber is 1 to 11 μm, the gaps in the base material are fine and uniform, so there is less powder falling off after forming the inorganic particle layer, and the surface coated with polyvinyl chloride resin tends to be flat. Furthermore, it becomes a fireproof sheet with excellent flexibility.
また、本発明におけるガラス繊維の繊維長は、１～１５ｍｍであることが好ましく、２～１０ｍｍであることがより好ましく、３～６ｍｍであることがさらに好ましい。繊維長が１ｍｍ未満では、基材の強度が不足する場合があり、繊維長が１５ｍｍを超えた場合、基材の地合が悪くなる場合や柔軟性が悪化する場合がある。 Further, the fiber length of the glass fiber in the present invention is preferably 1 to 15 mm, more preferably 2 to 10 mm, and even more preferably 3 to 6 mm. If the fiber length is less than 1 mm, the strength of the base material may be insufficient, and if the fiber length exceeds 15 mm, the texture or flexibility of the base material may deteriorate.
また、ガラス繊維の含有率は、基材に含まれる全繊維成分に対して、７５～９５質量％であることが好ましく、８０～９３質量％であることがより好ましく、８５～９０質量％であることがさらに好ましい。含有率が７５質量％未満であると、耐火性又は不燃性が悪くなる場合があり、含有率が９５質量％を超えると、ガラス繊維同士の結合は弱いことから、基材強度が弱くなり、無機粒子層の塗工性が悪化する場合があり、さらに、基材の繊維の隙間が大きくなるため、ポリ塩化ビニル樹脂塗工表面の平坦性が損なわれる場合がある。 Further, the content of glass fiber is preferably 75 to 95% by mass, more preferably 80 to 93% by mass, and 85 to 90% by mass based on the total fiber components contained in the base material. It is even more preferable that there be. If the content is less than 75% by mass, fire resistance or nonflammability may deteriorate, and if the content exceeds 95% by mass, the bond between glass fibers is weak, so the strength of the base material is weakened, The coating properties of the inorganic particle layer may deteriorate, and furthermore, the gaps between the fibers of the base material may become large, which may impair the flatness of the surface coated with the polyvinyl chloride resin.
本発明に用いるバインダー繊維は湿熱接着性バインダー繊維である。湿熱接着性バインダー繊維とは、湿潤状態において、ある温度で繊維状態から流動、又は容易に変形して接着機能を発現する繊維のことを言う。具体的には、熱水（例えば、８０～１２０℃程度）で軟化して自己接着、又は他の繊維に接着可能な熱可塑性繊維であり、例えば、ポリビニル系繊維（ポリビニルピロリドン、ポリビニルエーテル、ポリビニルアルコール、ポリビニルアセタールなど）、セルロース系繊維（メチルセルロースなどのＣ１－３アルキルセルロース、ヒドロキシメチルセルロースなどのヒドロキシＣ１－３アルキルセルロース、カルボキシメチルセルロースなどのカルボキシＣ１－３アルキルセルロース、又はその塩など）、変性ビニル系共重合体からなる繊維（イソブチレン、スチレン、エチレン、ビニルエーテルなどのビニル系単量体と、無水マレイン酸などの不飽和カルボン酸、又は、その無水物との共重合体、又はその塩など）などが挙げられる。本発明に用いる湿熱接着性バインダー繊維としては、ポリビニル系繊維が好ましく、ポリビニルアルコール（ＰＶＡ）繊維がより好ましく、基材強度がより高くなり、また、繊維間に皮膜を形成しやすく、無機粒子を繊維間に保持しやすくなる。 The binder fiber used in the present invention is a wet heat adhesive binder fiber. The wet heat adhesive binder fiber refers to a fiber that flows or easily deforms from a fibrous state at a certain temperature in a wet state to exhibit an adhesive function. Specifically, it is a thermoplastic fiber that can be softened in hot water (e.g., about 80 to 120°C) and self-adhesive or can adhere to other fibers, such as polyvinyl fibers (polyvinyl pyrrolidone, polyvinyl ether, polyvinyl (alcohol, polyvinyl acetal, etc.), cellulose fibers (C1-3 alkyl cellulose such as methyl cellulose, hydroxy C1-3 alkyl cellulose such as hydroxymethyl cellulose, carboxy C1-3 alkyl cellulose such as carboxymethyl cellulose, or its salts, etc.), modified vinyl Fibers made of copolymers (copolymers of vinyl monomers such as isobutylene, styrene, ethylene, vinyl ether, and unsaturated carboxylic acids such as maleic anhydride, or their anhydrides, or salts thereof) Examples include. As the wet heat adhesive binder fiber used in the present invention, polyvinyl fiber is preferable, and polyvinyl alcohol (PVA) fiber is more preferable, since the base material strength is higher, it is easy to form a film between the fibers, and inorganic particles are It becomes easier to hold between the fibers.
本発明に用いる湿熱接着性バインダー繊維としては、架橋性官能基を有する化合物で変性された変性ポリビニルアルコール繊維、架橋剤を用いて紡糸時又は紡糸後に温和な条件下で架橋を行った架橋ポリビニルアルコール繊維が、低延伸糸に耐熱水性を付与することが可能となり、より好ましい。 The wet heat adhesive binder fibers used in the present invention include modified polyvinyl alcohol fibers modified with a compound having a crosslinkable functional group, and crosslinked polyvinyl alcohol fibers that are crosslinked under mild conditions during or after spinning using a crosslinking agent. The fibers are more preferable because they can impart hot water resistance to the low-drawn yarn.
架橋性官能基としては、シラノール基、カルボキシル基、メチロール基等が挙げられる。ｐＨ等を調整することによって、架橋性官能基を有する化合物で変性されたポリビニルアルコールを架橋させることなく水に溶解し、紡糸して、変性ポリビニルアルコール繊維を得ることができる。紡糸時又は紡糸後に、変性ポリビニルアルコール繊維を架橋させても良い。変性度は、好ましくは０．０１～１０ｍｏｌ％であり、より好ましくは、０．１～５ｍｏｌ％である。好適な例としては、シラノール変性ポリビニルアルコール（変性度０．１～２ｍｏｌ％）をアルカリ溶液（ｐＨ９～１３）に溶解し、該溶液を酸性（ｐＨ５～６）にすることにより架橋させつつ紡糸し、乾燥後熱処理して得られるシラノール変性ポリビニルアルコール繊維が挙げられる。 Examples of the crosslinkable functional group include a silanol group, a carboxyl group, and a methylol group. By adjusting the pH and the like, polyvinyl alcohol modified with a compound having a crosslinkable functional group can be dissolved in water without crosslinking and spun to obtain modified polyvinyl alcohol fibers. The modified polyvinyl alcohol fibers may be crosslinked during or after spinning. The degree of modification is preferably 0.01 to 10 mol%, more preferably 0.1 to 5 mol%. As a preferred example, silanol-modified polyvinyl alcohol (denaturation degree 0.1 to 2 mol%) is dissolved in an alkaline solution (pH 9 to 13), and the solution is made acidic (pH 5 to 6) to crosslink and spin. , silanol-modified polyvinyl alcohol fibers obtained by heat treatment after drying.
また、自己架橋性のない未変性ポリビニルアルコールを紡糸後、各種有機系又は無機系架橋剤を付与して架橋せしめる方法によって得られた、架橋ポリビニルアルコール繊維を用いることもできる。無機系架橋剤としては、リン酸、リン酸アンモニウム、硫酸アンモニウム、硫酸チタニル等が挙げられる。また、有機系架橋剤として、メチロール系、エポキシ系、イソシアネート系、アルデヒド系等の架橋剤が挙げられる。これらの架橋剤を未変性ポリビニルアルコール紡糸原液に添加して紡糸した後、又は、未変性ポリビニルアルコールを単独で紡糸して架橋剤含有浴を通した後、熱処理することで架橋を進行させることができる。また、これらの方法を併用することも可能である。 Furthermore, crosslinked polyvinyl alcohol fibers obtained by spinning unmodified polyvinyl alcohol without self-crosslinking properties and then applying various organic or inorganic crosslinking agents to crosslink the fibers can also be used. Examples of the inorganic crosslinking agent include phosphoric acid, ammonium phosphate, ammonium sulfate, and titanyl sulfate. Examples of organic crosslinking agents include methylol-based, epoxy-based, isocyanate-based, and aldehyde-based crosslinking agents. After these crosslinking agents are added to an unmodified polyvinyl alcohol spinning stock solution and spun, or after unmodified polyvinyl alcohol is spun alone and passed through a crosslinking agent-containing bath, crosslinking can be progressed by heat treatment. can. It is also possible to use these methods in combination.
本発明に用いる湿熱接着性バインダー繊維は上記に限定されるものではないが、シラノール変性ポリビニルアルコール繊維は、ガラス繊維との接着性がさらに高まるため、基材の湿潤引張強度をさらに高めることができるため、特に好ましい。 The wet heat adhesive binder fibers used in the present invention are not limited to those mentioned above, but silanol-modified polyvinyl alcohol fibers can further increase the adhesiveness with glass fibers, thereby further increasing the wet tensile strength of the base material. Therefore, it is particularly preferable.
湿熱接着性バインダー繊維の繊度は、０．１～５．６デシテックスであることが好ましく、０．４～２．２デシテックスであることがより好ましく、０．６～１．１デシテックスであることがさらに好ましい。繊度が０．１デシテックス未満の場合、繊維自体が非常に高価になり、また、基材が緻密で薄くなり過ぎる場合がある。一方、５．６デシテックスを超えた場合、ガラス繊維との接点が少なくなり、湿潤状態での強度維持が困難になる場合がある。また、均一な地合が取れない場合がある。湿熱接着性バインダー繊維の繊維長は、１～１５ｍｍであることが好ましく、２～１０ｍｍであることがより好ましく、３～５ｍｍであることがさらに好ましい。繊維長が１ｍｍ未満の場合、抄造時に抄紙ワイヤーから湿熱接着性バインダー繊維が抜け落ちる場合があり、十分な強度の耐火シートが得られない場合がある。一方、１５ｍｍを超えた場合、水に分散する際に湿熱接着性バインダー繊維がもつれる場合があり、耐火シートの地合が不均一になる場合がある。 The fineness of the wet heat adhesive binder fiber is preferably 0.1 to 5.6 dtex, more preferably 0.4 to 2.2 dtex, and preferably 0.6 to 1.1 dtex. More preferred. When the fineness is less than 0.1 decitex, the fiber itself becomes very expensive, and the base material may become dense and too thin. On the other hand, if it exceeds 5.6 dtex, the number of points of contact with the glass fibers will decrease, and it may be difficult to maintain the strength in a wet state. Moreover, it may not be possible to obtain a uniform texture. The fiber length of the wet heat adhesive binder fiber is preferably 1 to 15 mm, more preferably 2 to 10 mm, and even more preferably 3 to 5 mm. If the fiber length is less than 1 mm, the wet heat adhesive binder fibers may fall off from the papermaking wire during papermaking, and a fireproof sheet with sufficient strength may not be obtained. On the other hand, if it exceeds 15 mm, the wet heat adhesive binder fibers may become tangled when dispersed in water, and the formation of the fireproof sheet may become uneven.
湿熱接着性バインダー繊維の含有率は、基材に含まれる全繊維成分に対して、３～２０質量％であることが好ましく、４～１５質量％であることがより好ましく、５～１０質量％であることがさらに好ましい。湿熱接着性バインダー繊維が３質量％未満の場合、基材の強度が低下し、無機粒子層を塗工する際に断紙する場合やガラス繊維が脱落する場合がある。一方、湿熱接着性バインダー繊維の含有率が２０質量％を超えた場合、基材を湿式抄造法で抄紙する際、ドライヤーからの剥離性が悪化する場合があり、また、無機粒子層を塗工する際に、基材への浸透性が低下する場合があり、壁紙裏打ち用耐火シートの耐火性が悪化する場合がある。 The content of the moist heat adhesive binder fiber is preferably 3 to 20% by mass, more preferably 4 to 15% by mass, and 5 to 10% by mass based on the total fiber components contained in the base material. It is more preferable that If the content of the wet heat adhesive binder fiber is less than 3% by mass, the strength of the base material decreases, and paper breakage may occur or glass fibers may fall off when applying the inorganic particle layer. On the other hand, if the content of the wet heat adhesive binder fiber exceeds 20% by mass, the peelability from the dryer may deteriorate when the base material is made into paper using a wet papermaking method, and the inorganic particle layer may not be coated. When doing so, the permeability into the base material may decrease, and the fire resistance of the fire-resistant sheet for backing wallpaper may deteriorate.
本発明に用いるフィブリル化耐熱性繊維としては、全芳香族ポリアミド、全芳香族ポリエステル、ポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリフェニレンスルフィド、ポリベンゾイミダゾール、ポリ－ｐ－フェニレンベンゾビスチアゾール、ポリ－ｐ－フェニレンベンゾビスオキサゾール、ポリテトラフルオロエチレン等の耐熱性樹脂からなるフィブリル化耐熱性繊維が挙げられる。これらの中でも、親水性が高く、フィブリル化しやすい全芳香族ポリアミドのフィブリル化耐熱性繊維が好ましい。 The fibrillated heat-resistant fibers used in the present invention include fully aromatic polyamide, fully aromatic polyester, polyimide, polyamideimide, polyetheretherketone, polyphenylene sulfide, polybenzimidazole, poly-p-phenylenebenzobisthiazole, poly- Examples include fibrillated heat-resistant fibers made of heat-resistant resins such as p-phenylenebenzobisoxazole and polytetrafluoroethylene. Among these, fibrillated heat-resistant fibers made of wholly aromatic polyamide, which are highly hydrophilic and easily fibrillated, are preferred.
このような全芳香族ポリアミドの代表的な例としては、ポリ（ｍ－フェニレンイソフタルアミド）、ポリ（ｍ－フェニレンテレフタルアミド）、ポリ（ｐ－フェニレンテレフタルアミド）、ポリ（ｐ－フェニレンイソフタルアミド）、ポリ（４，４′－オキシジフェニレンイソフタルアミド）、ポリ（４，４′－オキシジフェニレンテレフタルアミド）、ポリ（ｍ－ベンズアミド）、ポリ（ｐ－ベンズアミド）などが挙げられるが、これらのコポリマーであっても良いし、また、少量の芳香族基以外の成分を含んだものであっても良い。 Typical examples of such wholly aromatic polyamides include poly(m-phenylene isophthalamide), poly(m-phenylene terephthalamide), poly(p-phenylene terephthalamide), and poly(p-phenylene isophthalamide). , poly(4,4'-oxydiphenylene isophthalamide), poly(4,4'-oxydiphenylene terephthalamide), poly(m-benzamide), poly(p-benzamide), etc. It may be a copolymer, or it may contain a small amount of components other than aromatic groups.
また、全芳香族ポリアミドのフィブリル化耐熱性繊維は、抄紙機を用いて紙に似た構造物を作ることができる多数のフィブリル部を有する繊維状、薄膜状、又はリボン状構造を持っており、芳香族系重合体の溶液を沈殿剤中に導入して、微細な粒子として沈殿させて得られるものでも良い。 In addition, fully aromatic polyamide fibrillated heat-resistant fibers have a fibrous, film-like, or ribbon-like structure with multiple fibrils that can be used on a paper machine to create paper-like structures. Alternatively, it may be obtained by introducing a solution of an aromatic polymer into a precipitant and precipitating it as fine particles.
本発明において、基材に含まれる全繊維成分に対して、フィブリル化耐熱性繊維の含有率は２質量％以上１０質量％以下であることが好ましく、３質量％以上８質量％以下であることがより好ましく、３．５質量％以上６質量％以下であることがさらに好ましく、３．５質量％以上５質量％以下であることが特に好ましい。フィブリル化耐熱性繊維の含有率が１０質量％を超えた場合、基材が薄くなりやすく、基材の空隙が減少するため、無機粒子層が基材表面に形成されやすく、ポリ塩化ビニル樹脂塗工表面の平坦性は良化するものの、耐火シートの柔軟性が損なわれる場合や無機粒子の粉落ちが悪化する場合がある。また、耐火性や不燃性が低下する場合がある。一方、フィブリル化耐熱性繊維の含有率が２質量％未満である場合、フィブリル化耐熱性繊維間やフィブリル化耐熱性繊維とガラス繊維との緻密なネットワーク構造が形成されにくく、湿潤引張強度の向上効果が発現しにくくなる。また、基材の空隙が増大するため、ポリ塩化ビニル樹脂が基材内部に入り込みやすくなり、ポリ塩化ビニル樹脂塗工表面の平坦性は悪化する場合がある。 In the present invention, the content of fibrillated heat-resistant fibers is preferably 2% by mass or more and 10% by mass or less, and 3% by mass or more and 8% by mass or less, based on the total fiber components contained in the base material. is more preferable, more preferably 3.5% by mass or more and 6% by mass or less, particularly preferably 3.5% by mass or more and 5% by mass or less. If the content of the fibrillated heat-resistant fiber exceeds 10% by mass, the base material tends to become thinner, the voids in the base material decrease, and an inorganic particle layer is likely to be formed on the surface of the base material, resulting in a polyvinyl chloride resin coating. Although the flatness of the processed surface is improved, the flexibility of the fireproof sheet may be impaired and the shedding of inorganic particles may be worsened. In addition, fire resistance and nonflammability may decrease. On the other hand, when the content of fibrillated heat-resistant fibers is less than 2% by mass, it is difficult to form a dense network structure between fibrillated heat-resistant fibers or between fibrillated heat-resistant fibers and glass fibers, and the wet tensile strength is improved. It becomes difficult to express the effect. Furthermore, since the voids in the base material increase, the polyvinyl chloride resin tends to enter the inside of the base material, and the flatness of the surface coated with the polyvinyl chloride resin may deteriorate.
本発明におけるフィブリル化耐熱性繊維の変法濾水度は４０ｍｌ以上であることが好ましく、より好ましくは５０ｍｌ以上７００ｍｌ以下であり、さらに好ましくは１００ｍｌ以上６００ｍｌ以下であり、特に好ましくは３００ｍｌ以上４５０ｍｌ以下である。変法濾水度が７００ｍｌを超えた場合、フィブリル化があまり進んでいないため、ガラス繊維との絡み合いが少なくなるため、湿潤引張強度の向上効果が低下する場合がある。また、ガラス繊維間の空隙が広がりやすくなるため、無機粒子層が不均一となり、ポリ塩化ビニル樹脂塗工表面の平坦性が悪化する場合がある。一方、変法濾水度が４０ｍｌ未満の場合、フィブリル化耐熱性繊維のファイン分が増えて、基材から脱落する割合が増え、歩留まりが低下する場合がある。また、繊維のフィブリル化処理に時間が掛かり、非常に高価なものになる。また、基材が薄くなりやすく、高密度化しやすくなるため、無機粒子層形成用塗工液が内部に浸透しにくくなり、耐火性が悪化する場合がある。 The modified method freeness of the fibrillated heat-resistant fiber in the present invention is preferably 40 ml or more, more preferably 50 ml or more and 700 ml or less, even more preferably 100 ml or more and 600 ml or less, particularly preferably 300 ml or more and 450 ml or less. It is. When the modified freeness exceeds 700 ml, fibrillation has not progressed so much that entanglement with glass fibers is reduced, and the effect of improving wet tensile strength may be reduced. Furthermore, since the voids between the glass fibers tend to expand, the inorganic particle layer becomes non-uniform, and the flatness of the surface coated with the polyvinyl chloride resin may deteriorate. On the other hand, if the modified freeness is less than 40 ml, the fine content of the fibrillated heat-resistant fibers increases, the rate at which they fall off from the base material increases, and the yield may decrease. Furthermore, fibrillating the fibers takes time and is very expensive. Furthermore, since the base material tends to become thinner and more dense, it becomes difficult for the coating liquid for forming an inorganic particle layer to penetrate inside, and fire resistance may deteriorate.
本発明において、変法濾水度とは、ふるい板として線径０．１４ｍｍ、目開き０．１８ｍｍの８０メッシュ金網を用い、試料濃度を０．１％にした以外はＪＩＳ Ｐ８１２１－２：２０１２に準拠して測定した値のことである。 In the present invention, modified freeness refers to JIS P8121-2:2012 except that an 80-mesh wire mesh with a wire diameter of 0.14 mm and an opening of 0.18 mm was used as the sieve plate, and the sample concentration was 0.1%. This is the value measured in accordance with the .
本発明のフィブリル化耐熱性繊維において、質量加重平均繊維長は、０．０２ｍｍ以上１．５０ｍｍ以下であることが好ましい。また、長さ加重平均繊維長は、０．０２ｍｍ以上１．００ｍｍ以下であることが好ましい。平均繊維長が好ましい範囲よりも短い場合、基材からフィブリル化耐熱性繊維が脱落する場合がある。平均繊維長が好ましい範囲よりも長い場合、繊維の離解が悪くなり、分散不良が発生しやすくなる。 In the fibrillated heat-resistant fiber of the present invention, the mass weighted average fiber length is preferably 0.02 mm or more and 1.50 mm or less. Further, the length weighted average fiber length is preferably 0.02 mm or more and 1.00 mm or less. If the average fiber length is shorter than the preferred range, the fibrillated heat-resistant fibers may fall off from the base material. If the average fiber length is longer than the preferred range, fiber disintegration will be poor and poor dispersion will likely occur.
フィブリル化耐熱性繊維が、上記の質量加重平均繊維長と長さ加重平均繊維長を持つ場合、基材に含まれるフィブリル化耐熱性繊維の含有率が少ない場合でも、フィブリル化耐熱性繊維間やフィブリル化耐熱性繊維とガラス繊維との間において、繊維による緻密なネットワーク構造が形成され、湿潤引張強度が高く、無機粒子塗工液の浸透性や液保持性を高めることができる基材が得られやすくなる。 If the fibrillated heat-resistant fibers have the above mass-weighted average fiber length and length-weighted average fiber length, even if the content of the fibrillated heat-resistant fibers in the base material is small, the fibrillated heat-resistant fibers will A dense network structure is formed between the fibrillated heat-resistant fibers and the glass fibers, resulting in a base material with high wet tensile strength and enhanced permeability and liquid retention of inorganic particle coating liquids. become more susceptible to
フィブリル化耐熱性繊維の平均繊維幅は、０．５μｍ以上４０μｍ以下が好ましく、３μｍ以上３５μｍ以下がより好ましく、５μｍ以上３０μｍ以下がさらに好ましい。平均繊維幅が４０μｍを超えた場合、フィブリル化耐熱性繊維とガラス繊維の絡み合いが減少するため、湿潤引張強度が低下する場合があり、平均繊維幅が０．５μｍ未満の場合、基材からフィブリル化耐熱性繊維が脱落するようになり、交点が増え過ぎるために、湿熱接着性バインダー繊維を増やさないと、湿潤引張強度が低下する場合がある。 The average fiber width of the fibrillated heat-resistant fibers is preferably 0.5 μm or more and 40 μm or less, more preferably 3 μm or more and 35 μm or less, and even more preferably 5 μm or more and 30 μm or less. If the average fiber width exceeds 40 μm, the wet tensile strength may decrease due to the reduced entanglement of fibrillated heat-resistant fibers and glass fibers. If the average fiber width is less than 0.5 μm, fibrillation from the base material may decrease. If the wet heat adhesive binder fibers are not increased, the wet tensile strength may decrease because the heat-resistant fibers tend to fall off and the number of intersections increases too much.
本発明において、フィブリル化耐熱性繊維の質量加重平均繊維長、長さ加重平均繊維長及び平均繊維幅は、ＫａｊａａｎｉＦｉｂｅｒＬａｂＶ３．５（Ｍｅｔｓｏ Ａｕｔｏｍａｔｉｏｎ社製）を使用して、投影繊維長（Ｐｒｏｊ）モードにおいて測定した質量加重平均繊維長（Ｌ（ｗ））、長さ加重平均繊維長（Ｌ（ｌ））及び繊維幅である。 In the present invention, the mass-weighted average fiber length, length-weighted average fiber length, and average fiber width of the fibrillated heat-resistant fibers are determined in projected fiber length (Proj) mode using Kajaani FiberLab V3.5 (manufactured by Metso Automation). These are the measured mass-weighted average fiber length (L(w)), length-weighted average fiber length (L(l)), and fiber width.
フィブリル化耐熱性繊維は、耐熱性繊維をリファイナー、ビーター、ミル、摩砕装置、高速の回転刃によりせん断力を与える回転式ホモジナイザー、高速の回転する円筒の内刃と固定された外刃との間でせん断力を生じる二重円筒式の高速ホモジナイザー、超音波による衝撃で微細化する超音波破砕器、繊維懸濁液に少なくとも２０ＭＰａの圧力差を与えて小径のオリフィスを通過させて高速度とし、これを衝突させて急減速することにより、繊維にせん断力、切断力を加える高圧ホモジナイザー等を用いて処理することによって得ることができる。 Fibrillated heat-resistant fibers can be produced using heat-resistant fibers in refiners, beaters, mills, trituration devices, rotary homogenizers that apply shearing force using high-speed rotating blades, and high-speed rotating cylindrical inner blades and fixed outer blades. A double cylindrical high-speed homogenizer that generates shear force between the fibers, an ultrasonic crusher that atomizes the fibers by impacting them with ultrasonic waves, and a pressure difference of at least 20 MPa to the fiber suspension to make it pass through a small diameter orifice to achieve high speed. It can be obtained by processing using a high-pressure homogenizer or the like that applies shearing force and cutting force to the fibers by colliding them and rapidly decelerating them.
本発明において、ガラス繊維、湿熱接着性バインダー繊維、フィブリル化耐熱性繊維に加えて、必要に応じて、性能を阻害しない範囲で、各種繊維を配合することができる。その結果、さらに細かい空隙部を増やすことができ、無機粒子の保持性や壁紙裏打ち用耐火シートの強度を向上させることができる。このような繊維としては、レーヨン、キュプラ、リヨセル繊維等の再生繊維、アセテート、トリアセテート、プロミックス等の半合成繊維、ポリオレフィン系、ポリアミド系、ポリアクリル系、ビニロン系、ビニリデン、ポリ塩化ビニル、ポリエステル系、ベンゾエート、ポリクラール、フェノール、メラミン、フラン、尿素、アニリン、不飽和ポリエステル、フッ素、シリコーン、これらの誘導体等の合成樹脂繊維、金属繊維、炭素繊維、アルミナ、シリカ、セラミックス、岩石繊維等の無機繊維を加えることができる。 In the present invention, in addition to glass fibers, wet heat adhesive binder fibers, and fibrillated heat-resistant fibers, various fibers may be blended as needed within a range that does not impede performance. As a result, the number of finer voids can be increased, and the retention of inorganic particles and the strength of the fireproof sheet for backing wallpaper can be improved. Such fibers include recycled fibers such as rayon, cupro, and lyocell fibers, semi-synthetic fibers such as acetate, triacetate, and promix, polyolefins, polyamides, polyacrylics, vinylon, vinylidene, polyvinyl chloride, and polyester. Synthetic resin fibers such as benzoate, polychlor, phenol, melamine, furan, urea, aniline, unsaturated polyester, fluorine, silicone, and derivatives thereof, inorganic fibers such as metal fibers, carbon fibers, alumina, silica, ceramics, rock fibers, etc. Fiber can be added.
合成樹脂繊維は、単一の樹脂からなる繊維（単繊維）であっても良いし、２種以上の樹脂からなる複合繊維であっても良い。また、本発明の壁紙裏打ち用耐火シートに含まれる合成樹脂繊維は、１種でも良いし、２種以上を組み合わせて使用しても良い。複合繊維としては、芯鞘型、偏芯型、サイドバイサイド型、海島型、オレンジ型、多重バイメタル型が挙げられる。 The synthetic resin fiber may be a fiber (single fiber) made of a single resin, or a composite fiber made of two or more resins. Moreover, the number of synthetic resin fibers contained in the fireproof sheet for wallpaper lining of the present invention may be one type, or two or more types may be used in combination. Examples of composite fibers include core-sheath type, eccentric type, side-by-side type, sea-island type, orange type, and multi-bimetal type.
本発明において、基材の厚みは、０．２ｍｍ以上であることが好ましく、０．３ｍｍ以上であることがより好ましく、０．４ｍｍ以上であることがさらに好ましい。また、１．０ｍｍ以下であることが好ましく、０．８ｍｍ以下であることがより好ましく、０．６ｍｍ以下であることがさらに好ましい。基材の厚みを上記の範囲とした場合において、本発明における基材では、抄紙工程や塗工工程で必要な引張強度を維持できるため、基材の抄造性も含め、各工程での作業性が良好なものとなる。基材の厚みが１．０ｍｍを超えると、壁紙裏打ち用耐火シートとして、柔軟性が損なわれて、取り扱い難くなる場合がある。基材の厚みが０．２０ｍｍ未満であると、基材の空隙が大きくなり、塗工し難くなり、また、無機粒子層を多く塗工する必要があり、粉落ちが増える場合や柔軟性が悪化する場合がある。 In the present invention, the thickness of the base material is preferably 0.2 mm or more, more preferably 0.3 mm or more, and even more preferably 0.4 mm or more. Moreover, it is preferably 1.0 mm or less, more preferably 0.8 mm or less, and even more preferably 0.6 mm or less. When the thickness of the base material is within the above range, the base material of the present invention can maintain the tensile strength required in the paper making process and the coating process, so the workability in each process including the papermaking properties of the base material is improved. becomes good. If the thickness of the base material exceeds 1.0 mm, the flexibility of the fireproof sheet for wallpaper lining may be impaired, making it difficult to handle. If the thickness of the base material is less than 0.20 mm, the voids in the base material will become large, making it difficult to coat, and it will also be necessary to coat a large number of inorganic particle layers, which may increase powder fall or reduce flexibility. It may get worse.
本発明における基材の密度は、０．０７ｇ／ｃｍ３以上であることが好ましく、０．１０ｇ／ｃｍ３以上であることがより好ましい。また、０．３０ｇ／ｃｍ３以下であることが好ましく、０．２０ｇ／ｃｍ３以下であることがより好ましい。密度が０．０７ｇ／ｃｍ３未満である場合、基材の引張強度が弱くなり過ぎて、基材の取り扱い時や塗工時に破損するおそれがあり、０．３０ｇ／ｃｍ３を超えた場合、基材の柔軟性が悪化して、抄紙のリーラーで巻き取り難くなる場合や無機粒子層の塗工量が低下する場合がある。 The density of the base material in the present invention is preferably 0.07 g/cm 3 or more, more preferably 0.10 g/cm 3 or more. Further, it is preferably 0.30 g/cm 3 or less, more preferably 0.20 g/cm 3 or less. If the density is less than 0.07 g/cm 3 , the tensile strength of the base material becomes too weak and there is a risk of damage during handling or coating, and if the density exceeds 0.30 g/cm 3 , The flexibility of the base material may deteriorate, making it difficult to wind it up with a paper reeler, or the coating amount of the inorganic particle layer may decrease.
本発明における基材は、湿式抄造法（抄紙法）によって製造される湿式不織布であることが好ましい。湿式抄造法は繊維を水に分散して均一な抄紙スラリーとし、この抄紙スラリーを抄紙機で抄きあげて湿式不織布を製造する。抄紙機としては、円網抄紙機、長網抄紙機、傾斜型抄紙機、傾斜短網抄紙機、これらの複合機が挙げられる。また、複数のヘッドボックスを有し、ワイヤー上で湿紙を重ね合わせる抄紙機にて製造することができる。抄紙スラリーには、繊維原料の他に、必要に応じて、分散剤、紙力増強剤、増粘剤、無機填料、有機填料、消泡剤などを適宜添加することができる。抄紙スラリーの固形分濃度は、０．５～０．００１質量％程度であることが好ましい。この抄紙スラリーを、さらに所定濃度に希釈してから抄造し、湿紙ウェブを得る。ついで、抄造された湿紙ウェブは、プレスロールなどでニップされ、ついで、ヤンキードライヤーを使用し、湿熱接着性バインダー繊維を溶融させて、強度を発現させる。ヤンキードライヤーにて乾燥することにより、乾燥された表面は平滑となり、表面の凹凸が少ない面を形成できる。その他、補助乾燥として、熱風乾燥機、加熱ロール、赤外線ヒーターなどの加熱装置を併用しても問題ない。この時の乾燥温度としては、湿紙ウェブの水分が十分に除去でき、湿熱接着性バインダー繊維により強度を発現できる温度とすることが好ましい。 The base material in the present invention is preferably a wet nonwoven fabric manufactured by a wet papermaking method (papermaking method). In the wet papermaking method, fibers are dispersed in water to form a uniform papermaking slurry, and this papermaking slurry is processed using a paper machine to produce a wet nonwoven fabric. Examples of the paper machine include a cylinder paper machine, a fourdrinier paper machine, an inclined paper machine, an inclined short-mesh paper machine, and a combination machine thereof. It can also be manufactured using a paper machine that has a plurality of head boxes and stacks wet paper on a wire. In addition to the fiber raw material, a dispersant, a paper strength enhancer, a thickener, an inorganic filler, an organic filler, an antifoaming agent, and the like can be appropriately added to the papermaking slurry, if necessary. The solid content concentration of the papermaking slurry is preferably about 0.5 to 0.001% by mass. This papermaking slurry is further diluted to a predetermined concentration and then subjected to papermaking to obtain a wet paper web. The paper-formed wet paper web is then nipped with press rolls or the like, and then a Yankee dryer is used to melt the wet heat adhesive binder fibers to develop strength. By drying with a Yankee dryer, the dried surface becomes smooth and a surface with few surface irregularities can be formed. In addition, there is no problem even if a heating device such as a hot air dryer, heating roll, or infrared heater is used in combination as auxiliary drying. The drying temperature at this time is preferably a temperature at which moisture from the wet paper web can be sufficiently removed and strength can be developed by the wet heat adhesive binder fibers.
本発明において、無機粒子層は、無機粒子と無機バインダーを含有している層である。この無機粒子層が、基材に含有される繊維の表面全体を被覆しており、また、基材の空隙に充填されていることによって、耐火シートの耐火性と不燃性の効果が得られる。さらに、ポリ塩化ビニル樹脂の浸透性が抑えられ、塗工表面の平坦性が良好となる。 In the present invention, the inorganic particle layer is a layer containing inorganic particles and an inorganic binder. This inorganic particle layer covers the entire surface of the fibers contained in the base material and fills the voids in the base material, thereby providing the fireproof and noncombustible effects of the fireproof sheet. Furthermore, the permeability of the polyvinyl chloride resin is suppressed, and the flatness of the coated surface is improved.
図１は、無機粒子層が壁紙裏打ち用耐火シートに含有される繊維の表面を被覆している表面観察画像であり、電子顕微鏡（ＳＥＭ）観察写真である。基材に含有される繊維である、ガラス繊維及びフィブリル化耐熱性繊維と図１では確認できないが、湿熱接着性バインダー繊維の表面全体が、無機粒子（カオリン）及び無機バインダー（セピオライト）を含有している無機粒子層によって被覆されている。繊維の表面全体が無機粒子によって覆われることによって、耐火シートの耐火性が発現する。 FIG. 1 is a surface observation image showing that an inorganic particle layer covers the surface of fibers contained in a fireproof sheet for wallpaper lining, and is an electron microscope (SEM) observation photograph. Although it cannot be confirmed in Figure 1 that the fibers contained in the base material are glass fibers and fibrillated heat-resistant fibers, the entire surface of the wet heat adhesive binder fibers contains inorganic particles (kaolin) and an inorganic binder (sepiolite). coated with a layer of inorganic particles. The fire resistance of the fire resistant sheet is developed by covering the entire surface of the fibers with inorganic particles.
無機粒子としては、水酸化アルミニウム、水酸化酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、二水和石膏、アルミン酸三カルシウム、クレー、カオリン、焼成カオリン、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、タルク、二酸化チタン等の水分散性の良い無機粒子が使用できる。上記無機粒子は、単独で使用しても良いし、２種以上組み合わせて使用しても良い Inorganic particles include aluminum hydroxide, aluminum hydroxide oxide, magnesium hydroxide, calcium hydroxide, gypsum dihydrate, tricalcium aluminate, clay, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, barium carbonate, talc, Inorganic particles with good water dispersibility such as titanium dioxide can be used. The above inorganic particles may be used alone or in combination of two or more types.
無機粒子の中でも、水酸化酸化アルミニウム、クレー、カオリン、焼成カオリン、炭酸塩系の無機粒子は、火炎が当たった際に無機粒子が固化し、耐火シートから無機粒子が脱落することを防止できるため好ましい。さらに、水酸化酸化アルミニウム、クレー、カオリン、焼成カオリンは、耐火シートを高温化で保持した場合でも、耐火性と不燃性に優れ、耐火シートの強度を維持できるため、より好ましい。 Among inorganic particles, aluminum hydroxide oxide, clay, kaolin, calcined kaolin, and carbonate-based inorganic particles solidify when exposed to flame and can prevent the inorganic particles from falling off the fireproof sheet. preferable. Furthermore, aluminum hydroxide oxide, clay, kaolin, and calcined kaolin are more preferable because they have excellent fire resistance and noncombustibility and can maintain the strength of the fire resistant sheet even when the fire resistant sheet is maintained at high temperatures.
本発明において、無機粒子の粒子径は、０．０８μｍ以上２．００μｍ以下であることが好ましく、０．３０μｍ以上１．５０μｍ以下であることがより好ましく、０．４０μｍ以上１．００μｍ以下であることがさらに好ましい。粒子径が２．００μｍを超えると、壁紙裏打ち用耐火シートの耐火性が悪化する場合や粉落ちや高温下に曝した際の断熱性が悪化する場合がある。一方、粒子径が０．０８μｍ未満の場合、無機粒子を分散する際に増粘しやすく、分散し難くなり、基材に塗工した場合、無機粒子が基材から脱落しやすくなる場合や、脱落を防ぐために無機バインダーを増量する必要があり、耐火シートの柔軟性が損なわれる場合がある。なお、本発明で言う粒子径とは、無機粒子のＳＥＭ写真から得られた無機粒子の面積から真円の直径を換算した値である。 In the present invention, the particle size of the inorganic particles is preferably 0.08 μm or more and 2.00 μm or less, more preferably 0.30 μm or more and 1.50 μm or less, and 0.40 μm or more and 1.00 μm or less. It is even more preferable. If the particle size exceeds 2.00 μm, the fire resistance of the fireproof sheet for wallpaper lining may deteriorate, powder may fall off, or the heat insulation properties may deteriorate when exposed to high temperatures. On the other hand, if the particle size is less than 0.08 μm, the inorganic particles tend to increase in viscosity and become difficult to disperse, and when coated on a substrate, the inorganic particles may easily fall off from the substrate. It is necessary to increase the amount of inorganic binder to prevent it from falling off, which may impair the flexibility of the fireproof sheet. In addition, the particle diameter as used in the present invention is a value obtained by converting the diameter of a perfect circle from the area of the inorganic particles obtained from a SEM photograph of the inorganic particles.
本発明において、無機粒子層は無機バインダーを含む。無機バインダーとしては、例えば、セピオライト、コロイダルシリカ、水ガラス、アルミナゾル、ベントナイトなどが挙げられる。上記無機バインダーは、単独で使用しても良いし、２種以上組み合わせて使用しても良い。 In the present invention, the inorganic particle layer contains an inorganic binder. Examples of the inorganic binder include sepiolite, colloidal silica, water glass, alumina sol, and bentonite. The above inorganic binders may be used alone or in combination of two or more.
本発明において、無機粒子層に含まれる無機バインダーの含有率は、無機粒子の総量に対して、２質量％以上１００質量％以下であることが好ましく、５質量％以上５０質量％以下であることがより好ましく、１０質量％以上３０質量％以下であることがさらに好ましい。無機バインダーの含有率が２質量％未満の場合、無機粒子が基材から脱落しやすくなる場合がある。また、無機バインダーの含有率が１００質量％を超えた場合、無機粒子の塗工性が悪化する場合がある。 In the present invention, the content of the inorganic binder contained in the inorganic particle layer is preferably 2% by mass or more and 100% by mass or less, and 5% by mass or more and 50% by mass or less, based on the total amount of inorganic particles. is more preferable, and even more preferably 10% by mass or more and 30% by mass or less. When the content of the inorganic binder is less than 2% by mass, the inorganic particles may easily fall off from the base material. Furthermore, if the content of the inorganic binder exceeds 100% by mass, the coating properties of the inorganic particles may deteriorate.
無機粒子層形成用塗工液を調製するための媒体としては、無機バインダーや無機粒子を均一に溶解又は分散できるものであれば特に限定されない。例えば、トルエン等の芳香族炭化水素類、テトラヒドロフラン等のエーテル類、メチルエチルケトン等のケトン類、イソプロピルアルコール等のアルコール類、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド、水等を必要に応じて用いることができる。また、使用する媒体は、基材を膨張させない媒体又は基材を溶解しない媒体が好ましい。 The medium for preparing the coating liquid for forming an inorganic particle layer is not particularly limited as long as it can uniformly dissolve or disperse the inorganic binder and inorganic particles. For example, aromatic hydrocarbons such as toluene, ethers such as tetrahydrofuran, ketones such as methyl ethyl ketone, alcohols such as isopropyl alcohol, N-methyl-2-pyrrolidone (NMP), dimethylacetamide, dimethylformamide, dimethyl sulfoxide, Water etc. can be used as necessary. Further, the medium used is preferably a medium that does not expand the base material or a medium that does not dissolve the base material.
無機粒子層の含有率は、「無機粒子層の塗工量（ｇ／ｍ２）／基材坪量（ｇ／ｍ２）×１００」で算出される値であり、９０質量％以上が好ましく、１００質量％以上がより好ましく、１３０質量％以上がさらに好ましい。無機粒子層の含有率が９０質量％以上であれば、壁紙裏打ち用耐火シートに火炎を当てた場合でも、耐火シートの溶融や損傷がほとんどない。一方、無機粒子層の含有率は１６０質量％未満が好ましい。無機粒子層の含有率が高いほど、耐火シートの厚みが増加し、耐火性と不燃性は高くなるが、無機粒子層の含有率が１６０質量％以上の場合、粉落ちが発生する場合や耐火シートの柔軟性が損なわれる場合がある。 The content of the inorganic particle layer is a value calculated by "coating amount of inorganic particle layer (g/m 2 )/base weight (g/m 2 ) x 100", and is preferably 90% by mass or more. , more preferably 100% by mass or more, and still more preferably 130% by mass or more. If the content of the inorganic particle layer is 90% by mass or more, even when the fireproof sheet for wallpaper lining is exposed to flame, the fireproof sheet will hardly melt or be damaged. On the other hand, the content of the inorganic particle layer is preferably less than 160% by mass. The higher the content of the inorganic particle layer, the thicker the fireproof sheet becomes, and the higher the fire resistance and noncombustibility become. However, if the content of the inorganic particle layer is 160% by mass or more, powder drop may occur or the fireproof sheet may become thicker. The flexibility of the sheet may be impaired.
無機粒子層を形成するために、無機粒子を基材に塗工する装置としては、各種の塗工装置を用いることができる。例えば、２ロールサイズプレス、ゲートロールコーター、グラビアコーター、ダイコーター、リップコーター、ブレードコーター、カーテンコーター、エアーナイフコーター、ロッドコーター、キスタッチコーター、ディップコーター等の含浸、又は塗工装置による各種コーターを用いることができるが、これに限定されるものではない。 Various coating devices can be used to coat inorganic particles onto a base material to form an inorganic particle layer. For example, impregnation such as 2-roll size press, gate roll coater, gravure coater, die coater, lip coater, blade coater, curtain coater, air knife coater, rod coater, kiss touch coater, dip coater, or various coaters using coating equipment. can be used, but is not limited to this.
本発明において、無機粒子層には、前記無機粒子及び無機バインダーの他に、ポリアクリル酸、カルボキシメチルセルロースナトリウム等の各種分散剤、塗工液の液安定性を増すため、ヒドロキシエチルセルロース、カルボキシメチルセルロースナトリウム、ポリエチレンオキサイド等の各種増粘剤、各種保水剤、各種の濡れ剤、防腐剤、消泡剤等の各種添加剤を、必要に応じて添加することもできる。一般に、媒体として有機溶剤を使用した非水系塗工液は表面張力が低く、媒体として水を用いた水系塗工液の表面張力は高い。本発明の基材は、塗工液の受理性が高いため、非水系塗工液も水系塗工液も、両方共に問題なく塗工することができるが、本発明において、媒体として水のみを用いた水系塗工液を使用することが好ましい。 In the present invention, the inorganic particle layer includes, in addition to the inorganic particles and inorganic binder, various dispersants such as polyacrylic acid and sodium carboxymethylcellulose, and hydroxyethylcellulose and sodium carboxymethylcellulose to increase the stability of the coating solution. , various thickeners such as polyethylene oxide, various water retention agents, various wetting agents, preservatives, antifoaming agents, and other various additives may be added as necessary. Generally, non-aqueous coating liquids using an organic solvent as a medium have a low surface tension, while aqueous coating liquids using water as a medium have a high surface tension. Since the substrate of the present invention has high receptivity to coating liquids, it can be coated with both non-aqueous coating liquids and aqueous coating liquids without any problem. However, in the present invention, only water is used as the medium. It is preferable to use the same aqueous coating liquid as previously used.
本発明において、壁紙裏打ち用耐火シートの少なくとも片側の面を共焦点レーザー顕微鏡によって表面粗さを計測して得られるコア部のレベル差Ｓｋが５５μｍ以下であることが好ましく、５０μｍ以下であることがより好ましく、４５μｍ以下であることがさらに好ましい。また、Ｓｋは２５μｍ以上であることが好ましく、３０μｍ以上であることがより好ましく、３５μｍ以上であることがさらに好ましい。そして、ポリ塩化ビニル樹脂は、Ｓｋが５５μｍ以下である面に塗工されることが好ましい。ポリ塩化ビニル樹脂の塗工では、発泡ポリ塩化ビニル樹脂を塗工し、乾燥・ゲル化させた後、発泡させる。本発明の壁紙裏打ち用耐火シートの少なくとも片側の面のＳｋが５５μｍ以下である場合、ポリ塩化ビニル樹脂塗工表面の平坦性が良好となる。さらに、無機粒子層の粉落ちが少なく、柔軟性と耐火性と不燃性を兼ね備えた壁紙裏打ち用耐火シートが得られやすくなる。Ｓｋが５５μｍを超えた場合、ポリ塩化ビニル樹脂塗工表面の平坦性が悪化する場合がある。一方、Ｓｋが２５μｍ未満の場合、ポリ塩化ビニル樹脂塗工表面の平坦性が良好で、耐火性や不燃性も良好であるが、壁紙裏打ち用耐火シートとして柔軟性が損なわれる場合がある。 In the present invention, the level difference Sk of the core portion obtained by measuring the surface roughness of at least one side of the fireproof sheet for wallpaper lining using a confocal laser microscope is preferably 55 μm or less, and preferably 50 μm or less. More preferably, it is 45 μm or less. Further, Sk is preferably 25 μm or more, more preferably 30 μm or more, and even more preferably 35 μm or more. The polyvinyl chloride resin is preferably applied to a surface having a Sk of 55 μm or less. When applying polyvinyl chloride resin, foamed polyvinyl chloride resin is applied, dried and gelled, and then foamed. When the Sk of at least one side of the fireproof sheet for wallpaper lining of the present invention is 55 μm or less, the flatness of the surface coated with polyvinyl chloride resin will be good. Furthermore, there is less powder falling off of the inorganic particle layer, making it easier to obtain a fireproof sheet for wallpaper lining that has flexibility, fire resistance, and noncombustibility. When Sk exceeds 55 μm, the flatness of the polyvinyl chloride resin coated surface may deteriorate. On the other hand, when Sk is less than 25 μm, the flatness of the polyvinyl chloride resin coated surface is good, and the fire resistance and nonflammability are also good, but the flexibility as a fire-resistant sheet for wallpaper lining may be impaired.
本明細書において、「コア部のレベル差Ｓｋ」は、表面粗さを比較する指標であり、ＩＳＯ２５１７８に準拠したコア部の上側レベルと下側レベルとの差である。Ｓｋの測定方法を説明する。 In this specification, "core level difference Sk" is an index for comparing surface roughness, and is the difference between the upper level and lower level of the core based on ISO25178. The method of measuring Sk will be explained.
（１）壁紙裏打ち用耐火シートの写真撮影
壁紙裏打ち用耐火シートを幅４５ｍｍ×長さ６０ｍｍに断裁して試料とする。断裁した壁紙裏打ち用耐火シートの写真を、キーエンス社製共焦点レーザー顕微鏡ＶＫ－Ｘ１０５０（製品名）を用いて、以下の条件で観察する。
(1) Photographing the fireproof sheet for wallpaper lining The fireproof sheet for wallpaper lining was cut into 45 mm width x 60 mm length to use as a sample. A photograph of the cut fireproof sheet for wallpaper lining is observed using a confocal laser microscope VK-X1050 (product name) manufactured by Keyence Corporation under the following conditions.
「ＶＫ観察アプリケーション」の「形状計測」の「簡易測定」で、同軸照明で壁紙裏打ち用耐火シートを照らし、撮影倍率２０倍で観察する。「ナビゲーション画像作成」を行い、「連結測定」の「連結領域の指定方法」として「始点と長さ」を選び、撮影サイズを「横：３０００μｍ×縦：２０００μｍ」に指定し、写真撮影位置を決定して、測定を開始する。 Using "Simple measurement" in "Shape measurement" of the "VK observation application", illuminate the fireproof sheet for wallpaper lining with coaxial lighting and observe at 20x magnification. Perform "Navigation image creation", select "Start point and length" as "Connection area specification method" of "Connection measurement", specify the shooting size as "Width: 3000 μm x Height: 2000 μm", and set the photo shooting position. Decide and start measurement.
（２）画像補正
得られた壁紙裏打ち用耐火シートの写真を「マルチファイル解析アプリケーション」で開き、以下の順で画像補正処理を行う。
(2) Image correction Open the obtained photo of the fireproof sheet for wallpaper lining in a "multi-file analysis application" and perform image correction processing in the following order.
面形状補正：補正方法は「うねり除去」、指定方法は「補正の強さ」を選び、補正の強さを「５」に設定して面形状補正を行う。 Surface shape correction: Select "Waviness removal" as the correction method, "Correction strength" as the specification method, set the correction strength to "5", and perform surface shape correction.
（３）表面粗さ計測
計測領域として「全領域」を指定し、Ｓｋを計測する。一つの壁紙裏打ち用耐火シートについて、５箇所で本測定を実施し、５箇所におけるＳｋの平均値を算出する。
(3) Surface roughness measurement Specify "entire area" as the measurement area and measure Sk. For one wallpaper lining fireproof sheet, the actual measurement is carried out at 5 locations, and the average value of Sk at the 5 locations is calculated.
表面粗さ計測の詳細設定条件を表１に記載する。 Detailed setting conditions for surface roughness measurement are listed in Table 1.
壁紙裏打ち用耐火シートのＳｋを５５μｍ以下にする方法としては、
（Ｉ）繊維径の細いガラス繊維を使用する。
（II）湿熱接着性バインダー繊維を増量する。
（III）フィブリル化耐熱性繊維を増量する。
（IV）無機粒子層の塗工量を増量する。
（Ｖ）無機粒子層を、例えば、グラビアコーターやロッドコーター等の表面塗工方式で塗工する。
等が挙げられる。
As a method to reduce the Sk of fireproof sheet for wallpaper lining to 55μm or less,
(I) Use glass fibers with a narrow fiber diameter.
(II) Increase the amount of wet heat adhesive binder fiber.
(III) Increase the amount of fibrillated heat-resistant fibers.
(IV) Increase the coating amount of the inorganic particle layer.
(V) The inorganic particle layer is applied using a surface coating method such as a gravure coater or a rod coater.
etc.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。なお、実施例において百分率（％）及び部は、断りのない限り全て質量基準である。また、塗工量は絶乾塗工量である。 The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, in the examples, all percentages (%) and parts are based on mass unless otherwise specified. Moreover, the coating amount is an absolutely dry coating amount.
実施例１
＜基材の作製＞
ガラス繊維（日東紡績社製、繊維径６．５μｍ×繊維長６ｍｍ）を９０部、シラノール変性ＰＶＡ繊維（湿熱接着性バインダー繊維、商品名：ＳＰＧ０５６－１１、株式会社クラレ製、０．６デシテックス×３ｍｍ）を５部、パラ系全芳香族ポリアミド繊維のパルプ状物（平均繊維長１．７ｍｍ、平均繊維径１０μｍ）を、高圧ホモジナイザーを用いて変法濾水度２５０ｍｌまでフィブリル化させたフィブリル化耐熱性繊維５部を、パルパーにより水中に分散し、濃度０．５％の均一な抄紙スラリーを調成し、円網抄紙機を用いて湿紙ウェブを得て、表面温度１４０℃のヤンキードライヤーによって乾燥し、坪量５１．１ｇ／ｍ２、厚み０．３６７ｍｍの基材を作製した。
Example 1
<Preparation of base material>
90 parts of glass fiber (manufactured by Nitto Boseki Co., Ltd., fiber diameter 6.5 μm x fiber length 6 mm), silanol-modified PVA fiber (moisture heat adhesive binder fiber, trade name: SPG056-11, manufactured by Kuraray Co., Ltd., 0.6 decitex x Fibrillation was carried out by fibrillating 5 parts of para-based wholly aromatic polyamide fiber (average fiber length 1.7 mm, average fiber diameter 10 μm) using a high-pressure homogenizer to a modified freeness of 250 ml. 5 parts of heat-resistant fibers were dispersed in water using a pulper to prepare a uniform papermaking slurry with a concentration of 0.5%, a wet paper web was obtained using a cylinder paper machine, and a Yankee dryer with a surface temperature of 140°C was prepared. was dried to produce a base material having a basis weight of 51.1 g/m 2 and a thickness of 0.367 mm.
＜無機粒子層形成用塗工液の調製＞
カオリン（商品名：ＡＳＰ（登録商標） ＮＣ Ｘ－１、ＢＡＳＦ ＣＯＲＰＯＲＡＴＩＯＮ製）１００部と、水溶性アクリル酸系分散剤（商品名：アロン（登録商標）Ｔ－５０、東亞合成株式会社製）０．４部を水中に混合し十分撹拌し、カオリン分散液を調製した。ついで、セピオライト（商品名：ミルコン（登録商標）ＳＰ－２、昭和ＫＤＥ株式会社製）２０部と水溶性アクリル酸系分散剤（アロンＴ－５０）１．０部を水中に混合し十分撹拌し、セピオライト分散液を調製した。ついで、カオリン分散液全量とセピオライト分散液全量を混合、撹拌し、水で濃度を調整して、固形分濃度４０％の塗工液を調製した。
<Preparation of coating liquid for forming inorganic particle layer>
100 parts of kaolin (product name: ASP (registered trademark) NC .4 parts were mixed in water and thoroughly stirred to prepare a kaolin dispersion. Next, 20 parts of sepiolite (trade name: Mircon (registered trademark) SP-2, manufactured by Showa KDE Co., Ltd.) and 1.0 part of a water-soluble acrylic acid dispersant (Aron T-50) were mixed in water and thoroughly stirred. , a sepiolite dispersion was prepared. Next, the entire amount of the kaolin dispersion and the entire amount of the sepiolite dispersion were mixed and stirred, and the concentration was adjusted with water to prepare a coating solution with a solid content concentration of 40%.
＜壁紙裏打ち用耐火シートの作製＞
前記基材に、サイズプレスにて塗工液を含浸し、乾燥し、絶乾塗工量６４．４ｇ／ｍ２、総坪量１１５．５ｇ／ｍ２、厚み０．３３４ｍｍの壁紙裏打ち用耐火シートを作製した。
<Production of fireproof sheet for wallpaper lining>
The base material was impregnated with a coating liquid using a size press and dried to obtain a fireproof wallpaper lining with an absolute dry coating weight of 64.4 g/m 2 , a total basis weight of 115.5 g/m 2 , and a thickness of 0.334 mm. A sheet was produced.
実施例２
実施例１で使用したガラス繊維を９０部、実施例１で使用したシラノール変性ＰＶＡ繊維を５部と、パラ系全芳香族ポリアミド繊維のパルプ状物（平均繊維長１．７ｍｍ、平均繊維径１０μｍ）を、高圧ホモジナイザーを用いて変法濾水度５０ｍｌまでフィブリル化させたフィブリル化耐熱性繊維５部を、実施例１と同様な抄紙方法で、坪量５０．８ｇ／ｍ２、厚み０．３４５ｍｍの基材を作製した。
Example 2
90 parts of the glass fiber used in Example 1, 5 parts of the silanol-modified PVA fiber used in Example 1, and a pulp of para-based wholly aromatic polyamide fiber (average fiber length 1.7 mm, average fiber diameter 10 μm) ) was fibrillated to a modified freeness of 50 ml using a high-pressure homogenizer, and then 5 parts of fibrillated heat-resistant fibers were prepared using the same paper-making method as in Example 1 to have a basis weight of 50.8 g/m 2 and a thickness of 0.5 g/m 2 . A 345 mm base material was produced.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量６１．５ｇ／ｍ２、総坪量１１２．３ｇ／ｍ２、厚み０．３２８ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating liquid used in Example 1 using a size press and dried to give an absolutely dry coating weight of 61.5 g/m 2 , a total basis weight of 112.3 g/m 2 , and a thickness of 0.328 mm. A fireproof sheet for wallpaper lining was produced.
実施例３
実施例１で使用したガラス繊維を９０部、実施例１で使用したシラノール変性ＰＶＡ繊維を８部、実施例２で使用したフィブリル化耐熱性繊維２部を実施例１と同様な抄紙方法で、坪量５０．５ｇ／ｍ２、厚み０．３５５ｍｍの基材を作製した。
Example 3
90 parts of the glass fiber used in Example 1, 8 parts of the silanol-modified PVA fiber used in Example 1, and 2 parts of the fibrillated heat-resistant fiber used in Example 2 were prepared using the same papermaking method as in Example 1. A base material having a basis weight of 50.5 g/m 2 and a thickness of 0.355 mm was produced.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量６５．０ｇ／ｍ２、総坪量１１５．５ｇ／ｍ２、厚み０．３３８ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating solution used in Example 1 using a size press, and dried to give an absolute dry coating weight of 65.0 g/m 2 , a total basis weight of 115.5 g/m 2 , and a thickness of 0.338 mm. A fireproof sheet for wallpaper lining was produced.
実施例４
実施例１で使用したガラス繊維を８５部、実施例１で使用したシラノール変性ＰＶＡ繊維を５部、実施例１で使用したフィブリル化耐熱性繊維１０部を実施例１と同様な抄紙方法で、坪量５０．２ｇ／ｍ２、厚み０．３２８ｍｍの基材を作製した。
Example 4
85 parts of the glass fiber used in Example 1, 5 parts of the silanol-modified PVA fiber used in Example 1, and 10 parts of the fibrillated heat-resistant fiber used in Example 1 were prepared using the same papermaking method as in Example 1. A base material having a basis weight of 50.2 g/m 2 and a thickness of 0.328 mm was produced.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量６０．０ｇ／ｍ２、総坪量１１０．２ｇ／ｍ２、厚み０．３１１ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating liquid used in Example 1 using a size press, and dried to give an absolute dry coating weight of 60.0 g/m 2 , a total basis weight of 110.2 g/m 2 , and a thickness of 0.311 mm. A fireproof sheet for wallpaper lining was produced.
実施例５
実施例１で使用したガラス繊維を９０部、実施例１で使用したシラノール変性ＰＶＡ繊維を９部、実施例２で使用したフィブリル化耐熱性繊維１部を実施例１と同様な抄紙方法で、坪量５０．７ｇ／ｍ２、厚み０．３６２ｍｍの基材を作製した。
Example 5
90 parts of the glass fiber used in Example 1, 9 parts of the silanol-modified PVA fiber used in Example 1, and 1 part of the fibrillated heat-resistant fiber used in Example 2 were prepared using the same papermaking method as in Example 1. A base material having a basis weight of 50.7 g/m 2 and a thickness of 0.362 mm was produced.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量６６．５ｇ／ｍ２、総坪量１１７．２ｇ／ｍ２、厚み０．３５２ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating solution used in Example 1 using a size press and dried to give an absolute dry coating weight of 66.5 g/m 2 , a total basis weight of 117.2 g/m 2 , and a thickness of 0.352 mm. A fireproof sheet for wallpaper lining was produced.
実施例６
実施例１で使用したガラス繊維を８３部、実施例１で使用したシラノール変性ＰＶＡ繊維を５部、実施例１で使用したフィブリル化耐熱性繊維１２部を実施例１と同様な抄紙方法で、坪量５０．５ｇ／ｍ２、厚み０．３２５ｍｍの基材を作製した。
Example 6
83 parts of the glass fiber used in Example 1, 5 parts of the silanol-modified PVA fiber used in Example 1, and 12 parts of the fibrillated heat-resistant fiber used in Example 1 were prepared using the same papermaking method as in Example 1. A base material having a basis weight of 50.5 g/m 2 and a thickness of 0.325 mm was produced.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量６０．１ｇ／ｍ２、総坪量１１０．６ｇ／ｍ２、厚み０．３０６ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating liquid used in Example 1 using a size press, and dried to give an absolute dry coating weight of 60.1 g/m 2 , a total basis weight of 110.6 g/m 2 , and a thickness of 0.306 mm. A fireproof sheet for wallpaper lining was produced.
実施例７
ガラス繊維（繊維径４．０μｍ×繊維長３ｍｍ）を９０部、実施例１で使用したシラノール変性ＰＶＡ繊維を５部、実施例１で使用したフィブリル化耐熱性繊維５部を実施例１と同様な抄紙方法で、坪量５０．５ｇ／ｍ２、厚み０．３３８ｍｍの基材を作製した。
Example 7
90 parts of glass fiber (fiber diameter 4.0 μm x fiber length 3 mm), 5 parts of the silanol-modified PVA fiber used in Example 1, and 5 parts of the fibrillated heat-resistant fiber used in Example 1 as in Example 1. A base material having a basis weight of 50.5 g/m 2 and a thickness of 0.338 mm was produced using a paper making method.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量６２．０ｇ／ｍ２、総坪量１１２．５ｇ／ｍ２、厚み０．３１６ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating liquid used in Example 1 using a size press and dried to give an absolutely dry coating weight of 62.0 g/m 2 , a total basis weight of 112.5 g/m 2 , and a thickness of 0.316 mm. A fireproof sheet for wallpaper lining was produced.
実施例８
実施例１で使用したガラス繊維を９０部、実施例１で使用したシラノール変性ＰＶＡ繊維を５部、実施例１で使用したフィブリル化耐熱性繊維５部を実施例１と同様な抄紙方法で、坪量５１．１ｇ／ｍ２、厚み０．３６７ｍｍの基材を作製した。
Example 8
90 parts of the glass fiber used in Example 1, 5 parts of the silanol-modified PVA fiber used in Example 1, and 5 parts of the fibrillated heat-resistant fiber used in Example 1 were prepared using the same papermaking method as in Example 1. A base material having a basis weight of 51.1 g/m 2 and a thickness of 0.367 mm was produced.
この基材に実施例１で用いた塗工液に保水剤（商品名：ＳＮシックナー９２６、サンノプコ製）０．０８部を添加した塗工液をコンマコーターにて、表裏それぞれ１回ずつ表面塗工し、乾燥し、合計の絶乾塗工量７５．０ｇ／ｍ２、総坪量１２６．１ｇ／ｍ２、厚み０．３６８ｍｍの壁紙裏打ち用耐火シートを作製した。 Using a comma coater, coat the front and back surfaces of this substrate once with a coating solution prepared by adding 0.08 part of a water retention agent (product name: SN Thickener 926, manufactured by San Nopco) to the coating solution used in Example 1 using a comma coater. The mixture was coated and dried to produce a fireproof sheet for wallpaper lining having a total dry coating weight of 75.0 g/m 2 , a total basis weight of 126.1 g/m 2 and a thickness of 0.368 mm.
実施例９
実施例１で使用したガラス繊維を９０部、ＰＶＡ繊維（湿熱接着性バインダー繊維、商品名：ＶＰＢ１０７－１、株式会社クラレ製、１．１デシテックス×３ｍｍ）を５部、実施例１で使用したフィブリル化耐熱性繊維５部を、実施例１と同様な抄紙方法で、坪量５０．５ｇ／ｍ２、厚み０．３２２ｍｍの基材を作製した。
Example 9
90 parts of the glass fiber used in Example 1 and 5 parts of PVA fiber (wet heat adhesive binder fiber, trade name: VPB107-1, manufactured by Kuraray Co., Ltd., 1.1 decitex x 3 mm) were used in Example 1. A base material having a basis weight of 50.5 g/m 2 and a thickness of 0.322 mm was prepared using 5 parts of fibrillated heat-resistant fibers using the same paper-making method as in Example 1.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量６５．０ｇ／ｍ２、総坪量１１５．５ｇ／ｍ２、厚み０．３８５ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating liquid used in Example 1 using a size press and dried to give an absolutely dry coating weight of 65.0 g/m 2 , a total basis weight of 115.5 g/m 2 , and a thickness of 0.385 mm. A fireproof sheet for wallpaper lining was produced.
比較例１
実施例１で使用したガラス繊維９０部、実施例１で使用したシラノール変性ＰＶＡ繊維１０部とした以外、実施例１と同様な抄紙方法で坪量５０．１ｇ／ｍ２、厚み０．３１７ｍｍの基材を作製した。
Comparative example 1
A paper having a basis weight of 50.1 g/m 2 and a thickness of 0.317 mm was made in the same manner as in Example 1, except that 90 parts of the glass fiber used in Example 1 and 10 parts of the silanol-modified PVA fiber used in Example 1 were used. A base material was prepared.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量５５．２ｇ／ｍ２、総坪量１０５．３ｇ／ｍ２、厚み０．３０８ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating solution used in Example 1 using a size press and dried to give an absolute dry coating weight of 55.2 g/m 2 , a total basis weight of 105.3 g/m 2 , and a thickness of 0.308 mm. A fireproof sheet for wallpaper lining was produced.
比較例２
実施例１で使用したガラス繊維９０部、メタ系全芳香族ポリアミド繊維（商品名：メタワン、Ｈｕｖｉｓ製）のパルプ状物を、高速ミキサーを用いて変法濾水度１５０ｍｌまでフィブリル化させたフィブリル化耐熱性繊維１０部とした以外、実施例１と同様な抄紙方法で坪量５０．５ｇ／ｍ２、厚み０．３７０ｍｍの基材を作製した。
Comparative example 2
Fibrils were obtained by fibrillating 90 parts of the glass fiber used in Example 1 and the pulp of the meta-based wholly aromatic polyamide fiber (trade name: Meta One, manufactured by Huvis) to a modified method freeness of 150 ml using a high-speed mixer. A base material having a basis weight of 50.5 g/m 2 and a thickness of 0.370 mm was produced using the same paper making method as in Example 1 except that 10 parts of the heat-resistant fibers were used.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量５８．０ｇ／ｍ２、総坪量１０８．５ｇ／ｍ２、厚み０．３５０ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating solution used in Example 1 using a size press and dried to give an absolute dry coating weight of 58.0 g/m 2 , a total basis weight of 108.5 g/m 2 , and a thickness of 0.350 mm. A fireproof sheet for wallpaper lining was produced.
比較例３
実施例１で使用したガラス繊維９０部、実施例９で使用したＰＶＡ繊維５部、未叩解ＮＢＫＰを５部とした以外、実施例１と同様な抄紙方法で坪量５０．５ｇ／ｍ２、厚み０．３００ｍｍの基材を作製した。
Comparative example 3
Paper making method similar to Example 1 except that 90 parts of the glass fiber used in Example 1, 5 parts of the PVA fiber used in Example 9, and 5 parts of unbeaten NBKP was used, with a basis weight of 50.5 g/m 2 , A base material with a thickness of 0.300 mm was produced.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量５５．０ｇ／ｍ２、総坪量１０５．５ｇ／ｍ２、厚み０．３０５ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating solution used in Example 1 using a size press, and dried to give an absolute dry coating weight of 55.0 g/m 2 , a total basis weight of 105.5 g/m 2 , and a thickness of 0.305 mm. A fireproof sheet for wallpaper lining was produced.
比較例４
実施例１で使用したガラス繊維９０部、実施例１で使用したシラノール変性ＰＶＡ繊維５部、リファイナーを用いて平均繊維径１２μｍ、繊維長５ｍｍの溶剤紡糸セルロース繊維を微細化し、変法濾水度１００ｍｌに叩解されてなるフィブリル化セルロース繊維５部とした以外、実施例１と同様な抄紙方法で坪量５１．２ｇ／ｍ２、厚み０．２９３ｍｍの基材を作製した。
Comparative example 4
Using a refiner, 90 parts of the glass fiber used in Example 1, 5 parts of the silanol-modified PVA fiber used in Example 1, and a solvent-spun cellulose fiber with an average fiber diameter of 12 μm and a fiber length of 5 mm were refined, and the modified freeness was determined. A base material having a basis weight of 51.2 g/m 2 and a thickness of 0.293 mm was produced by the same papermaking method as in Example 1 except that 5 parts of fibrillated cellulose fibers were beaten to 100 ml.
この基材に実施例１で用いた塗工液をサイズプレスにて含浸し、乾燥し、絶乾塗工量５９．１ｇ／ｍ２、総坪量１１０．３ｇ／ｍ２、厚み０．２９８ｍｍの壁紙裏打ち用耐火シートを作製した。 This base material was impregnated with the coating liquid used in Example 1 using a size press, and dried to give an absolute dry coating weight of 59.1 g/m 2 , a total basis weight of 110.3 g/m 2 , and a thickness of 0.298 mm. A fireproof sheet for wallpaper lining was produced.
比較例５
無機粒子層形成用塗工液として、実施例１で使用したカオリン１００部と水溶性アクリル酸系分散剤０．４部と塩化ビニル系エマルジョン（商品名：ビニブラン（登録商標）２７８、固形分濃度４３％、日信化学工業株式会社製）２０部を水中で混合し十分撹拌し、固形分濃度４０％の塗工液を調製した。
Comparative example 5
As a coating liquid for forming an inorganic particle layer, 100 parts of kaolin used in Example 1, 0.4 parts of a water-soluble acrylic acid dispersant, and a vinyl chloride emulsion (trade name: Vinibran (registered trademark) 278, solid content concentration) were used. 43% (manufactured by Nissin Chemical Industry Co., Ltd.) in water and thoroughly stirred to prepare a coating liquid with a solid content concentration of 40%.
この塗工液を実施例１で作製した坪量５１．１ｇ／ｍ２、厚み０．３６７ｍｍの基材に、サイズプレスにて含浸し、乾燥し、絶乾塗工量６３．５ｇ／ｍ２、総坪量１１４．６ｇ／ｍ２、厚み０．３３８ｍｍの壁紙裏打ち用耐火シートを作製した。 This coating solution was impregnated into the base material prepared in Example 1 with a basis weight of 51.1 g/m 2 and a thickness of 0.367 mm using a size press and dried, with an absolute dry coating weight of 63.5 g/m 2 A fireproof sheet for wallpaper lining with a total basis weight of 114.6 g/m 2 and a thickness of 0.338 mm was produced.
実施例及び比較例の壁紙裏打ち用耐火シート用基材及び壁紙裏打ち用耐火シートについて、下記物性の測定と評価を行い、結果を表２に示した。 The following physical properties were measured and evaluated for the base materials for fireproof sheets for wallpaper lining and the fireproof sheets for wallpaper lining of Examples and Comparative Examples, and the results are shown in Table 2.
＜基材の坪量及び無機粒子層の塗工量＞
ＪＩＳ Ｐ８１２４：２０１１に準拠して、基材の坪量及び無機粒子層の塗工量を測定した。無機粒子層の塗工量は壁紙裏打ち用耐火シートの総坪量から基材の坪量を差し引いて算出した。
<Basic weight of base material and coating amount of inorganic particle layer>
The basis weight of the base material and the coating amount of the inorganic particle layer were measured in accordance with JIS P8124:2011. The coating amount of the inorganic particle layer was calculated by subtracting the basis weight of the base material from the total basis weight of the fireproof sheet for wallpaper lining.
＜基材及び壁紙裏打ち用耐火シートの厚み＞
ＪＩＳ Ｂ７５０２：２０１６に規定された外側マイクロメーターを用いて、５Ｎ荷重時の厚みを測定した。
<Thickness of base material and fireproof sheet for wallpaper lining>
The thickness at a load of 5N was measured using an outside micrometer specified in JIS B7502:2016.
＜コア部のレベル差Ｓｋ＞
上述した測定方法によって、各壁紙裏打ち用耐火シートにおいて、基材の乾燥時にヤンキードライヤーに接触している面を表面として、表面のＳｋを測定した。
<Level difference Sk in core section>
According to the measurement method described above, the Sk of the surface of each fireproof sheet for wallpaper lining was measured, with the surface in contact with the Yankee dryer when the base material was drying being taken as the front surface.
＜基材の引張強度＞
各基材について、長辺が流れ方向になるように、流れ方向２５０ｍｍ×幅方向５０ｍｍのサンプル片を５枚切り出し、卓上型万能試験機（株式会社エー・アンド・デイ製、商品名ＳＴＢ－１２２５Ｓ）を用いて、ＪＩＳ Ｐ８１１３：１９９８に準じて、引張速度１００ｍｍ／ｍｉｎで引張試験を行った。引張応力の最大値を「引張強度」とし、５枚の平均値とした。
<Tensile strength of base material>
For each base material, cut out five sample pieces measuring 250 mm in the flow direction x 50 mm in the width direction so that the long side is in the flow direction, and use a tabletop universal testing machine (manufactured by A&D Co., Ltd., product name STB-1225S). ), a tensile test was conducted at a tensile speed of 100 mm/min according to JIS P8113:1998. The maximum value of the tensile stress was defined as the "tensile strength", and the average value of the five sheets was taken.
＜基材の湿潤引張強度＞
各基材について、長辺が流れ方向になるように、流れ方向２５０ｍｍ×幅方向５０ｍｍのサンプル片を５枚切り出し、２３℃のイオン交換水中に３分間浸漬し、サンプル片を取り出した後、表面のイオン交換水をキムタオル（登録商標）で軽く拭き取り、卓上型万能試験機（株式会社エー・アンド・デイ製、商品名ＳＴＢ－１２２５Ｓ）を用いて、ＪＩＳ Ｐ８１１３：１９９８に準じて、引張速度１００ｍｍ／ｍｉｎで引張試験を行った。引張応力の最大値を「湿潤引張強度」とし、５枚の平均値とした。
<Wet tensile strength of base material>
For each base material, cut out five sample pieces measuring 250 mm in the flow direction x 50 mm in the width direction so that the long side is in the flow direction, immerse them in 23°C ion exchange water for 3 minutes, take out the sample pieces, and then Lightly wipe off the ion-exchanged water with Kim Towel (registered trademark), and test at a tensile speed of 100 mm using a tabletop universal testing machine (manufactured by A&D Co., Ltd., product name STB-1225S) in accordance with JIS P8113:1998. A tensile test was conducted at /min. The maximum value of the tensile stress was defined as the "wet tensile strength", and the average value of the five sheets was taken as the "wet tensile strength".
＜無機粒子層の塗工性＞
基材に無機粒子層を形成する際の塗工しやすさを、次の評価基準で評価した。
<Coatability of inorganic particle layer>
The ease of coating when forming an inorganic particle layer on a base material was evaluated using the following evaluation criteria.
○：塗工液を塗工する際に、基材に断紙や亀裂や割れが発生しない場合
△：塗工液を塗工する際に、基材に断紙や亀裂や割れがたまに発生する場合
×：塗工液を塗工する際に、基材に断紙や亀裂や割れが発生する場合
○: Paper breaks, cracks, or cracks do not occur on the base material when applying the coating liquid. △: Paper breaks, cracks, or cracks occasionally occur on the base material when applying the coating liquid. Case ×: When paper breaks, cracks, or cracks occur on the base material when applying the coating liquid.
＜耐火性＞
壁紙裏打ち用耐火シートの耐火性の評価としては、各シートから幅方向１００ｍｍ×流れ方向１００ｍｍサイズの試験片を３枚切り出し、各試験片の中央部にバーナー（商品名：ラボバーナーＡＰＴＬ、株式会社フェニックスデント製）の火炎を５分間当てた。その後、火炎を当てた側の耐火シートの表面を目視にて観察し、次の評価基準で評価した。バーナーの火炎温度は、１０００℃であった。
<Fire resistance>
To evaluate the fire resistance of fireproof sheets for wallpaper lining, three test pieces with a size of 100 mm in the width direction x 100 mm in the machine direction were cut out from each sheet, and a burner (product name: Labo Burner APTL, Inc.) was placed in the center of each test piece. A flame (manufactured by Phoenix Dent) was applied for 5 minutes. Thereafter, the surface of the fireproof sheet on the side to which the flame was applied was visually observed and evaluated using the following evaluation criteria. The flame temperature of the burner was 1000°C.
○：耐火シートに穴や亀裂や溶融がない。
△：火炎を当てた耐火シートの表面に溶融や凹みがわずかに見られる。
×：耐火シートに穴や亀裂がある。
○: There are no holes, cracks, or melting in the fireproof sheet.
△: Slight melting and dents are observed on the surface of the fireproof sheet exposed to flame.
×: There are holes and cracks in the fireproof sheet.
＜不燃性＞
壁紙裏打ち用耐火シートを不燃性の評価としては、各シートから幅方向１００ｍｍ×流れ方向１００ｍｍサイズの試験片を２枚切り出し、各試験片を７５０℃±５℃に保持できる加熱電気炉の中に挿入し、次の評価基準で評価した。
<Nonflammability>
To evaluate the noncombustibility of fireproof sheets for wallpaper lining, cut out two test pieces with a size of 100 mm in the width direction x 100 mm in the machine direction from each sheet, and place each test piece in a heating electric furnace that can maintain the temperature at 750°C ± 5°C. It was inserted and evaluated using the following evaluation criteria.
○：挿入後、発火しない。
△：挿入後、一瞬発火する。
×：挿入後、シート表面が発火する。
○: No fire after insertion.
△: Fires momentarily after insertion.
×: After insertion, the sheet surface ignites.
＜ポリ塩化ビニル樹脂塗工表面の平坦性＞
上記の壁紙裏打ち用耐火シートを幅１５ｃｍ長さ２０ｃｍに裁断し、ガラス板の上に表面が上になるように載せ、表面に壁紙用の発泡ポリ塩化ビニルゾルをギャップ０．１５ｍｍのアプリケーターバーで塗工し、１５０℃の恒温熱風乾燥機で２５秒加熱し、ゲル化させた。その後、２２０℃の恒温熱風乾燥機で４０秒加熱し、発泡ポリ塩化ビニルゾルを発泡させた。上記の作成させた発泡塩ビ表面の凹凸を目視で観察し、次の評価基準で評価した。
<Flatness of polyvinyl chloride resin coating surface>
Cut the above fireproof sheet for wallpaper lining into pieces 15 cm wide and 20 cm long, place it on a glass plate with the surface facing up, and apply foamed polyvinyl chloride sol for wallpaper on the surface using an applicator bar with a gap of 0.15 mm. The mixture was heated for 25 seconds in a constant temperature hot air dryer at 150°C to form a gel. Thereafter, the foamed polyvinyl chloride sol was foamed by heating for 40 seconds in a constant temperature hot air dryer at 220°C. The irregularities on the surface of the foamed PVC produced above were visually observed and evaluated using the following evaluation criteria.
○：発泡面が平滑である。
△：発泡面に少し凹凸がある。
×：発泡面の凹凸が大きい。
○: The foamed surface is smooth.
△: The foamed surface is slightly uneven.
×: Large irregularities on the foamed surface.
＜粉落ち＞
上記の壁紙裏打ち用耐火シートの表面を手で触った際に、手に無機粒子が付着する状態と卓上ギロチンカッターでシートを裁断した際の粉落ちを目視で観察し、次の基準で評価した。
<Powder fall>
When touching the surface of the above-mentioned fireproof sheet for wallpaper lining, we visually observed the state in which inorganic particles adhered to the hand and the amount of powder falling off when the sheet was cut with a tabletop guillotine cutter, and evaluated using the following criteria. .
○：手に無機粒子が付着しないし、裁断しても粉落ちしない。
△：手に無機粒子がうっすらと付着し、１０枚以上裁断すると、粉落ちが見られる。
×；手に無機粒子が付着し、裁断すると、粉落ちが見られる。
○: Inorganic particles do not adhere to hands, and powder does not fall off even when cut.
Δ: Inorganic particles slightly adhere to the hands, and when 10 or more sheets are cut, powder is observed to fall off.
×: Inorganic particles adhere to hands, and when cut, powder is observed to fall off.
＜柔軟性＞
上記の壁紙裏打ち用耐火シートを塗工後、コーターのリーラーで外周直径１０ｃｍの紙管に巻き付けた際に、シートの様子を目視で観察し、次の基準で評価した。
<Flexibility>
After coating the above-mentioned fireproof sheet for lining wallpaper, when it was wound around a paper tube with an outer diameter of 10 cm using a reeler of a coater, the state of the sheet was visually observed and evaluated according to the following criteria.
○：紙管にきれいに巻き付けることができる。
△：紙管の巻き付け直後、シートが紙管外周から多少浮き気味、もしくはシワが見られるが、しばらくするときれいに巻くことができる。
×：紙管にきれいに巻き付けることができず、大きな浮きや割れやシワが発生する。
○: Can be wrapped neatly around a paper tube.
Δ: Immediately after winding the paper tube, the sheet slightly floats or wrinkles are seen from the outer periphery of the paper tube, but it can be wound neatly after a while.
×: The paper cannot be wrapped neatly around the paper tube, and large lifts, cracks, and wrinkles occur.
＜無機粒子層の繊維表面の被覆＞
壁紙裏打ち用耐火シートの無機粒子層が繊維の表面を被覆しているかどうかの評価は、ＳＥＭ観察によって、次の基準で評価した。
<Coating of fiber surface with inorganic particle layer>
Whether the inorganic particle layer of the fireproof sheet for wallpaper lining covered the surface of the fibers was evaluated by SEM observation using the following criteria.
○：無機粒子層が繊維の表面を被覆している。
×：無機粒子層が繊維の表面を被覆していない。
○: An inorganic particle layer covers the surface of the fiber.
×: The inorganic particle layer does not cover the surface of the fiber.
表２に示した通り、実施例１～９で作製した壁紙裏打ち用耐火シートは、基材と無機粒子層とを含有し、該基材がガラス繊維と湿熱接着性バインダー繊維とフィブリル化耐熱性繊維を含有し、該無機粒子層が無機粒子と無機バインダーを含有し、且つ、該無機粒子層が、該基材に含有される繊維の表面を被覆している。ガラス繊維とフィブリル化耐熱性繊維が緻密に絡み合い、その絡み合った交点を湿熱接着性バインダー繊維が固定するため、湿潤引張強度が強くなり、無機粒子層形成用塗工液を塗工しても、断紙等が発生することがほとんどなかった。また、実施例１～９で作製した壁紙裏打ち用耐火シートは、耐火性と不燃性に優れていた。さらに、ポリ塩化ビニル樹脂塗工表面の平坦性が良好で、無機粒子層からの粉落ちが少なく、柔軟性に優れていた。 As shown in Table 2, the fireproof sheets for wallpaper lining produced in Examples 1 to 9 contained a base material and an inorganic particle layer, and the base material contained glass fibers, moist heat adhesive binder fibers, and fibrillated heat resistant sheets. The base material contains fibers, the inorganic particle layer contains inorganic particles and an inorganic binder, and the inorganic particle layer covers the surface of the fibers contained in the base material. Glass fibers and fibrillated heat-resistant fibers are tightly intertwined, and the wet heat adhesive binder fibers fix the intertwined intersections, resulting in strong wet tensile strength, even when coated with an inorganic particle layer forming coating solution. There were almost no occurrences of paper breaks. Furthermore, the fireproof sheets for wallpaper lining produced in Examples 1 to 9 had excellent fire resistance and nonflammability. Furthermore, the polyvinyl chloride resin coating surface had good flatness, little powder falling from the inorganic particle layer, and excellent flexibility.
実施例１と実施例９を比較すると、湿熱接着性バインダー繊維として、シラノール変性ポリビニルアルコール繊維を使用することで、湿潤引張強度はさらに良化し、無機粒子層の塗工性が向上することが判った。 Comparing Example 1 and Example 9, it was found that by using silanol-modified polyvinyl alcohol fiber as the wet heat adhesive binder fiber, the wet tensile strength was further improved and the coatability of the inorganic particle layer was improved. Ta.
実施例１と実施例２を比較すると、フィブリル化耐熱性繊維の変法濾水度を低くすると、ガラス繊維とフィブリル化耐熱性繊維の絡み合いが増加するため、湿潤引張強度が向上し、シートのコア部のレベル差Ｓｋが小さくなった。 Comparing Example 1 and Example 2, it is found that lowering the modified freeness of the fibrillated heat-resistant fibers increases the entanglement of the glass fibers and the fibrillated heat-resistant fibers, improving the wet tensile strength of the sheet. The level difference Sk in the core portion has become smaller.
実施例２と実施例３と実施例５を比較すると、フィブリル化耐熱性繊維の含有率が２質量％を下回ると、ガラス繊維とフィブリル化耐熱性繊維の絡み合いが低下するため、基材が厚くなり、無機粒子層の塗工性は問題ないものの、湿潤引張強度が低下した。また、フィブリル化耐熱性繊維の含有率が減少するほど、Ｓｋが大きくなり、ポリ塩化ビニル樹脂塗工表面は徐々に凹凸が見られるようになった。 Comparing Example 2, Example 3, and Example 5, when the content of fibrillated heat-resistant fibers is less than 2% by mass, the entanglement of glass fibers and fibrillated heat-resistant fibers decreases, resulting in a thick base material. Although there was no problem with the coating properties of the inorganic particle layer, the wet tensile strength decreased. Furthermore, as the content of fibrillated heat-resistant fibers decreased, Sk increased, and the surface coated with polyvinyl chloride resin gradually became uneven.
実施例１と実施例４と実施例６を比較すると、フィブリル化耐熱性繊維が増加するほど、Ｓｋが小さくなった。しかし、無機粒子層からの粉落ちが見られた。 Comparing Example 1, Example 4, and Example 6, the Sk became smaller as the amount of fibrillated heat-resistant fiber increased. However, powder falling from the inorganic particle layer was observed.
実施例１と実施例８を比較すると、無機粒子層を基材表面に表面塗工方式で塗工した方が、Ｓｋは小さくなった。しかし、耐火シートが硬くなり、コーターのリーラーで巻きにくくなった。 Comparing Example 1 and Example 8, Sk was smaller when the inorganic particle layer was applied to the surface of the base material using the surface coating method. However, the fireproof sheet became hard and became difficult to wind with the coater's reeler.
比較例１の壁紙裏打ち用耐火シートは、フィブリル化耐熱性繊維を含まない場合であるが、湿潤引張強度が低く、無機粒子層形成用塗工液を塗工する際に断紙等が発生した。７５０℃の加熱電気炉に挿入した際、表面が一瞬発火し、不燃性が不十分であった。また、Ｓｋ値が大きくなり、発泡ポリ塩化ビニル樹脂塗工表面に凹凸が見られた。また、粉落ちは発生しやすくなり、シートが硬くなり、コーターのリーラーで巻きにくくなった。 The fireproof sheet for wallpaper lining of Comparative Example 1 did not contain fibrillated heat-resistant fibers, but had low wet tensile strength and paper breakage occurred when applying the coating solution for forming an inorganic particle layer. . When inserted into a heating electric furnace at 750°C, the surface ignited momentarily, and the nonflammability was insufficient. In addition, the Sk value increased, and irregularities were observed on the foamed polyvinyl chloride resin coating surface. In addition, powder dropout was more likely to occur, and the sheet became hard, making it difficult to wind it with the coater's reeler.
比較例２の壁紙裏打ち用耐火シートは、湿熱接着性バインダー繊維を含まない場合であるが、引張強度と湿潤引張強度が共に低下したため、無機粒子層形成用塗工液を塗工する際に断紙等が発生した。また、Ｓｋが小さくなるが、粉落ちしやすくなった。 The fireproof sheet for wallpaper lining of Comparative Example 2 did not contain wet heat adhesive binder fibers, but both the tensile strength and the wet tensile strength decreased, so there was no disconnection when applying the coating solution for forming the inorganic particle layer. Paper etc. were generated. In addition, although Sk became smaller, powder fell off more easily.
比較例３と比較例４は、セルロース繊維を含む場合であるが、７５０℃の加熱電気炉に挿入した際、表面が一瞬発火し、不燃性が不十分であった。また、比較例３はフィブリル化繊維を含まないため、湿潤引張強度が低下し、無機粒子層形成用塗工液を塗工する際に断紙等が発生した。 Comparative Examples 3 and 4 contain cellulose fibers, but when inserted into a heating electric furnace at 750° C., the surface ignited momentarily and the nonflammability was insufficient. In addition, since Comparative Example 3 did not contain fibrillated fibers, the wet tensile strength decreased, and paper breakage etc. occurred when applying the coating liquid for forming an inorganic particle layer.
比較例５の壁紙裏打ち用耐火シートは、無機粒子層に有機系バインダーを使用した場合であるが、７５０℃の加熱電気炉に挿入した際、表面が発火し、不燃性が不十分であった。 The fireproof sheet for wallpaper lining of Comparative Example 5 used an organic binder in the inorganic particle layer, but when inserted into a heating electric furnace at 750°C, the surface caught fire and its nonflammability was insufficient. .
実施例３と実施例５を比較すると、Ｓｋが５５μｍ以下である場合、発泡塩化ビニル樹脂塗工表面の平坦性が良好になることが判る。 Comparing Example 3 and Example 5, it can be seen that when Sk is 55 μm or less, the flatness of the foamed vinyl chloride resin coated surface is improved.
本発明の壁紙裏打ち用耐火シートは、家屋等に使用される内装用の壁紙裏打ち用シートに関するものであり、発泡ポリ塩化ビニル（発泡塩ビゾル）塗工の壁紙裏打ち用シートに好適に使用できる。 The fireproof sheet for wallpaper lining of the present invention relates to a wallpaper lining sheet for interior decoration used in houses, etc., and can be suitably used as a wallpaper lining sheet coated with foamed polyvinyl chloride (foamed vinyl chloride sol).
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